Use of organic and organometallic high dielectric constant material for improved energy storage devices and associated methods

ABSTRACT

A dielectric material is provided. The dielectric material includes at least one layer of a substantially continuous phase material. The material is selected from the group consisting of an organic, organometallic, or combination thereof in which the substantially continuous phase material has delocalized electrons.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a continuation of U.S. patent application Ser. No. 13/747,441,filed Jan. 22, 2013, which is a continuation of InternationalApplication No. PCT/US11/044912 filed Jul. 21, 2011, which claimspriority to U.S. Provisional Patent Application No. 61/366,333 filed onJul. 21, 2010; the entire contents of which are hereby incorporated byreference in their entireties.

TECHNICAL FIELD

The present invention relates to ultra-high charge capacity dielectricmaterial (UHCC-dielectric material) for use in a dielectric material,associated fabrication methods, and applications of the dielectricmaterial and fabrication methods. The dielectric material enablessuperior energy storage per unit mass or per surface area given a fixedthickness compared to existing state of the art materials.

BACKGROUND

Electrical energy has been used for providing energy to automobiles.Among the advantages of electrical propulsion are its cleanliness andlack of emissions during driving, high efficiency, quietness, andreliability. During the early years of automotive development electricalpropulsion was a formidable competitor to the internal combustionengine.

The internal combustion engine had a decided advantage over electricmotors because of the greater onboard energy storage afforded by liquidfuel, especially petroleum distillates and gasoline. Early electricautomobiles had only a short range, typically less than 40 miles,followed by a lengthy charging cycle. By comparison, fossil fuel poweredvehicles can travel hundreds of miles and need only a quick refueling inorder to go another several hundred miles.

The significant drawback of electrically propelled automobiles has beenthe low energy density of the batteries used as a power source. Earlybatteries were usually lead acid type, which were very heavy and addedto the weight of the vehicle. Over the years, improvements have beenmade in battery technology to reduce the weight penalty, but progresshas not been sufficient to radically change the relative range ofelectrically powered automobiles versus their gasoline poweredcounterparts.

Recently, lithium ion batteries have been introduced which reduce theweight and increase the driving range of electric automobiles, but theyare very expensive so that their most promising application is in hybridautomobiles where a smaller battery is sufficient. The small batterymeans that the primary energy source is still a gasoline powered engine.

Capacitors store electric energy. A capacitor usually includes a pair ofelectrodes that are configured on each side of a dielectric material toincrease energy storage. The amount of energy stored by the capacitor isdirectly proportional to the dielectric constant. Thus the higher thedielectric constant, the greater the energy storage. Accordingly,efforts are being undertaken to develop dielectric materials with higherdielectric constants so that capacitors and related devices can be usedfor energy storage for powering devices and machinery including asautomobiles.

SUMMARY

This Summary is provided to introduce a selection of concepts in asimplified form that are further described below in the DetailedDescription of Illustrative Embodiments. This Summary is not intended toidentify key features or essential features of the claimed subjectmatter, nor is it intended to be used to limit the scope of the claimedsubject matter. Considerable work has been done on thin films of copperpthalocyanine which were prepared by sputtering or evaporation. Thereare several problems with using thin films, among which are a lowbreakdown voltage due to the thinness of films, and limited ability tomake composite films.

One or more experiments and investigations disclosed herein investigatedthick film structures with pthalocyanine, therefore, and successfullydeveloped methods of making thick films that would act as capacitorswith the ability to store charge hence ultra-high charge capacitorshaving capacitor like and battery like attributes.

Disclosed herein is the use of copper phthalocyanine particulatesembedded within organic vehicles to form a ultra high dielectricconstant k, and capacitors with ultra high capacitance and the abilityto hold charge for long periods of time. One or more capacitorsdisclosed herein may be made by dispersing copper phthalocyanineparticulates in a solvents and mixing the dispersion in a printingvehicle to form a green copper phthalocyanine dielectric. The greencopper phthalocyanine dielectric is applied over a conductive electrodeof a capacitor to form a thick film. The thick film copperphthalocyanine green dielectric layer is dried at 60 to 80 C andoptionally sintered at 150 to 200 degrees C. to form a continuous layer.The preparation steps are repeated if necessary. A top electrode isapplied over the bottom phthalocyanine dielectric structure of steps.This method has the advantage that large thickness dielectric layers canbe applied, enhancing the charge storage capability and increasing theresistance of the dielectric, whereas conventional methods of creating acopper phthalocyanine dielectric were limited when using an extremelythin dielectric layers prohibiting a large scale polarization and chargestorage.

A filler material can be added to the green paste of the noveldielectric to increase resistance.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing summary, as well as the following detailed description ofpreferred embodiments, is better understood when read in conjunctionwith the appended drawings. For the purposes of illustration, there isshown in the drawings exemplary embodiments; however, the presentlydisclosed invention is not limited to the specific methods andinstrumentalities disclosed. In the drawings:

FIG. 1 is an illustration of the organic vehicle according to at leastone embodiment of the invention, in which a solvent and a resin aremechanically stirred under heat to assist uniformity of the mix;

FIG. 2 is an illustration of a manner in which the solid dielectricparticulates are mixed with a solvent and the organic vehicle to form apaste of the novel dielectric material according to at least oneembodiment of the invention;

FIG. 3 is an illustration of a paste being roll milled to improvedispersion to form the printable paste of the novel dielectric material,according to at least one embodiment of the invention;

FIG. 4 graphically represents a controlled thermal profile to which thethick film green dielectric paste layer is subjected, according to atleast one embodiment of the invention;

FIG. 5A illustrates a first electrode according to at least oneembodiment of the invention;

FIG. 5B illustrates a film made of the novel dielectric havingultra-high dielectric constant applied to the first electrode of FIG. 5a;

FIG. 5C illustrates a second electrode applied to the film and firstelectrode of FIGS. 5a and 5 b;

FIG. 6 represents a cross-sectional view of a capacitor having first andsecond electrodes around a dried thick film having a substantiallycontinuous phase material there between, according to at least oneembodiment of the invention;

FIG. 7 represents a cross-sectional view of a capacitor having aninterface material layered between the dielectric film and the electrodefor each of the opposing electrodes, according to at least oneembodiment of the invention;

FIG. 8 represents a cross-sectional view of a capacitor having, betweenopposed electrodes, a substantially crystallized continuous phase of thenovel dielectric thick material, according to at least one embodiment ofthe invention;

FIG. 9 represents a cross-sectional view of a capacitor having, betweenopposed electrodes, the novel dielectric material with its dipolesinsubstantial alignment, according to at least one embodiment of theinvention;

FIG. 10 represents a cross-sectional view of a capacitor having, betweenopposed electrodes, the novel dielectric material with dielectricfillers, according to at least one embodiment of the invention;

FIG. 11 represents a cross-sectional view of a capacitor having, aninner layer embedded substantially in the center of capacitor and withinthe novel dielectric between opposed electrodes, a layered structureincluding a continuous phase material and dielectric fillers, accordingto at least one embodiment of the invention;

FIG. 12 represents a chemical structure of, phthalocyanine, according toat least one embodiment of the invention;

FIG. 13 represents a chemical structure of copper-phthalocyanine used inparticulates form to construct the novel dielectric;

FIG. 14 represents a chemical structure of Pyrene;

FIG. 15 represents a chemical structure of Fluorescein;

FIG. 16 represents a chemical structure of Anthrone;

FIG. 17 represents a chemical structure of an organometallic compound,according to at least one embodiment of the invention;

FIG. 18 is a diagrammatic representation of a parallel plate capacitorcharged under DC conditions;

FIG. 19A is a diagrammatic representation of a parallel plate capacitorcharged under AC conditions;

FIG. 19B is a diagrammatic representation of the parallel platecapacitor of FIG. 19a , with reversed field orientations;

FIG. 20 is a diagrammatic representation of a dielectric materialoccupying a volume between opposed electrodes and the formation ofdipoles within the material, according to at least one embodiment of theinvention;

FIG. 21 graphically represents a dielectric constant and a loss factoras dependent on frequency, according to at least one embodiment of theinvention;

FIG. 22A illustrates a capacitor having first electrode coated with aninterface layer made of a conductive Ink containing carbon, and a secondelectrode having a dielectric deposited thereon, according to at leastone embodiment of the invention;

FIG. 22B illustrates a capacitor having first electrode coated with aninterface layer made of a conductive Ink containing carbon, and a secondelectrode having a dielectric deposited thereon, according to at leastone embodiment of the invention;

FIG. 23 illustrates the novel dielectric material with a solvent isencapsulated between two opposed electrodes by a gasket, according to atleast one embodiment of the invention;

FIG. 24 illustrates a capacitor in which multiple first electrodes arecoupled to a larger single second electrode, according to at least oneembodiment of the invention;

FIG. 25A illustrates first and second opposed electrodes havingrespective dielectric layers with different chemistries;

FIG. 25B illustrates the dielectric layers of FIG. 25A mated to form acapacitor of increased resistance, capacitance and the half life byusing two chemistry variations of the novel dielectric compositions,according to at least one embodiment of the invention;

FIG. 26 illustrates a capacitive device having two dielectric layers ofdifferent compositions and held using a compression device, according toat least one embodiment of the invention;

FIG. 27A illustrates a capacitor exhibiting diode-like behavior,according to at least one embodiment of the invention where an aluminumelectrode coated with a aqueous ink containing carbon black;

FIG. 27B illustrates a capacitor exhibiting high capacitance having twoKovar electrodes coated with an aqueous ink containing carbon black,according to at least one embodiment of the invention;

FIG. 27C illustrates a capacitor exhibiting high capacitance having twoKovar electrodes coated with an aqueous ink containing carbon black andan inner layer of a dried aqueous ink containing carbon black, accordingto at least one embodiment of the invention;

FIG. 28 illustrates a capacitor having a perforated electrode, accordingto at least one embodiment of the invention;

FIG. 29 illustrates a capacitor having an inner dielectric layer lodgedbetween two thick film layers of the novel dielectric FIG. 30illustrates another capacitor having an inner layer that is a resin withhigh polarity (where the resin can be doped using carbon) according toat least one embodiment of the invention;

FIG. 31 is a graphical representation of experimental results inresistance and leakage current across a dielectric material to which avoltage range was applied;

FIG. 32 graphically represents the experimental results of severalchemistries tested in terms of charge decay which demonstrates theeffect of chemistry on the resistance of the dielectric;

FIG. 33 illustrates a capacitor having a metallic inner layer carryingno bias and positioned between two layers of the novel dielectric thatare disposed between two outer electrodes, according to at least oneembodiment of the invention;

FIG. 34 is a plan view of the capacitor of FIG. 33;

FIG. 35 is a schematic circuit diagram of an exemplary system used forcharging and discharging capacitors;

FIG. 36 graphically represents experimental results of the voltagedecays in time of two capacitors, one having a bridging layer (the innerlayer) and the other having no bridging layer;

FIG. 37 graphically represents experimental results of the voltagedecays in time of two capacitors having different concentrations ofBaTiO3 additive in their dielectric layers;

FIG. 38 graphically represents experimental results of the voltagedecays in time of a capacitor that was charged under heat in one caseand at room temperature in the other case applied heat during biasenables more charging as the saturation current dropped from 243 to 45Micro-Amps

FIG. 39 graphically represents experimental results of the voltage decayin time of a capacitor recharged until a saturation current wasachieved, as illustrated in the figure the charge storage capability isdemonstrated; furthermore, the rate of voltage decay is slower as timegoes by FIG. 40 graphically represents experimental results of thevoltage decays in time of capacitors having Kovar and aluminumelectrodes, the Kovar electrodes are better for building the capacitors;

FIG. 41 graphically represents experimental results of the voltagedecays in time of capacitors having a metallic inner layer and anorganic inner layer;

FIG. 42 graphically represents experimental results of the voltagedecays in time of a capacitor that was biased using two differentvoltages FIG. 43 graphically represents experimental results of thevoltage decay in time of a capacitor in which the voltage droppedrelatively quickly from a higher value to a lower value, at whichfurther decay was slowed; this illustrates the non linearity of thedielectric behavior and correlates with the increased resistance trendthat slows down decay at lower voltages;

FIG. 44A illustrates a capacitor having a passive metal inner-layerbetween external electrodes, according to at least one embodiment of theinvention;

FIG. 44B illustrates a capacitor having an active metal inner-layer(internal electrode) between external electrodes, according to at leastone embodiment of the invention;

FIG. 45 graphically represents experimental results of the voltagedecays in time of capacitors of FIGS. 44A and 44B; the passive metallicinner layer yields better results;

FIG. 46A illustrates a capacitor having a metal inner-layer and anorganic inner layer combined in the same capacitor, according to atleast one embodiment of the invention;

FIG. 46B is a plan view of the capacitor of FIG. 46A;

FIG. 47 illustrates a capacitor having five passive metallicinner-layers between external electrodes, according to at least oneembodiment of the invention;

FIG. 48 graphically represents experimental results of the voltage decayin time of the capacitor of FIG. 47 where a voltage build up to 10V wasdemonstrated;

FIG. 49 graphically represents experimental results of the voltagedecays in time of a capacitor discharged through various resistive loadsfrom 10M-Ohm to 20 k-Ohm, according to at least one embodiment of theinvention, FIG. 50 graphically represents experimental results of thevoltage decays in time of a capacitor according to at least oneembodiment of the invention and contrasted with the discharge of acommercially available electrolytic capacitor having 220 micro-Farads,each through the same resistance load;

FIG. 51 graphically represents experimental results of the voltagedecays in time of the capacitors investigated in FIG. 50, each throughanother resistance load that was different than that of FIG. 50;

FIG. 52 graphically represents experimental results of the voltagedecays in time of the capacitor of FIG. 47 and an electrolyticcapacitor, each through first and second resistance loads;

FIG. 53 graphically represents experimental results of the current flowsthrough a resistive load per unit time for the capacitor of FIG. 47,taken at several resistance load values, contrasted with the currentflow through a resistive load per unit time for an electrolyticcapacitor of 220 micro Farads;

FIG. 54 graphically represents experimental results of the voltagedecays in time of the capacitor of FIG. 47 through several resistanceloads;

FIG. 55 graphically represents the charging of the capacitor as it wasinvestigated in FIG. 54;

FIG. 56 contrasts the charging currents of a capacitor having 2 externalelectrodes and five metallic inner layers, according to at least oneembodiment of the invention, and a 1000 mF capacitor;

FIG. 57 graphically represents the cumulative charge output or currentintegration in mA-sec for a 1000 mF capacitor;

FIG. 58 graphically represents the cumulative charge output or currentintegration in mA-sec of the novel capacitor having two externalelectrodes and five metallic inner layers according to at least oneembodiment of the invention;

FIG. 59 contrasts the charge output in mA-sec for the novel capacitorhaving two external electrodes and five metal inner layers, according toat least one embodiment of the invention, and a 1000 mF capacitor;

FIG. 60 represents the charging of the novel capacitor having twoexternal electrodes and 5 metal inner layers, according to at least oneembodiment of the invention;

FIG. 61 graphically represents various voltage decay measurementsperformed on a capacitor having five metal inner layers, according to atleast one embodiment of the invention, and charged according to FIG. 60at various voltages including 100V, 50V, 11V and 5V;

FIG. 62 represents the charging of a capacitor having two externalelectrodes and five metal inner layers, according to at least oneembodiment of the invention, where the middle electrode was used as apositive pole and the two external electrodes were used as negativepoles;

FIG. 63 graphically represents current integration or total chargeoutput the novel capacitor having two external electrodes an five metalinner layers, that was biased using 100V charged according to the twodifferent charging arrangements of FIGS. 60 and 62; and

FIG. 64 graphically represents one or more capacitors for use with aphotovoltaic array according to one or more embodiments disclosedherein.

DETAILED DESCRIPTION

The presently disclosed invention is described with specificity to meetstatutory requirements. However, the description itself is not intendedto limit the scope of this patent. Rather, the inventors havecontemplated that the claimed invention might also be embodied in otherways, to include different steps or elements similar to the onesdescribed in this document, in conjunction with other present or futuretechnologies. Moreover, although the term “step” may be used herein toconnote different aspects of methods employed, the term should not beinterpreted as implying any particular order among or between varioussteps herein disclosed unless and except when the order of individualsteps is explicitly described.

According to at least one embodiment, one or more capacitors operate ator below 1 Hz, or may operate at as low as 0.00001 Hz, and are made byinner-layering special materials enabling extremely high charge storageat the molecular level. The inner-layered structure is stabilized toenable a macroscopic ultra-high charge storage with dielectric constantfar exceeding 2,000 reaching into the 100,000 range and in special cases(post further stabilization) in the 35,000,000 range and higher.

The ultra high energy storage capability achieved, for example, enablesfar ranging battery applications from Personal Digital Assistants andcomputers to automobiles.

When used in a low frequency setting with the application of electrodes,the one or more UHCC-dielectric materials allow for the fabrication ofone or more capacitor devices that may be used for battery applications.Such a device may operate at or below 10 Hz. In at least one embodiment,a capacitor device operates in a static conditions 0 Hz or below 0.1 Hzor 0.00001 Hz, and is constructed by preparing a paste of theun-processed dielectric material and subsequently applying at least onthick film and preferably multilayered thick film with a central innerlayer for bridging the two halves of the dielectric and matingelectrodes with each side of the formed layered dielectric structureswhile ensuring good electrical contact at the interface of thedielectric and the electrodes on each side to achieve high charge flow,charge build up and storage of said electrical charge at thesuper-capacitor level. In one or more embodiments, more than one layerof UHCC-dielectric material may be used.

The obtainment of a high dielectric constant (or high-K value) andsuperior charge storage per unit mass is enabled through the use of afamily of organic and/or organometallic materials having delocalizedelectrons and characteristically long relaxation times (more than aminute) under oscillating electric fields.

Novel layering leading to the obtainment of high-K values and minimalleakage currents consists of forming and stabilizing a thick film of asubstantially continuous phase out of the family of organic andorganometallic materials. The materials family can include organic andorganometallic semiconductors. The film can be made from the organicfamily alone or in combination with the family of organometallics.Conversely, the film can be made from the organometallic materialsfamily alone or in combination with the family of organic materials.

The organics and/or organometallics materials may be selected from agroup comprising Phthalocyanine, polycyclic aromatic hydrocarbon, PyreneBenzoquinoline, Fluorescein, Carbonyl, Unsaturated Ketone, Anthrone,Uranine, Rhodamine, compounds and/or related organometallics such asCopper-Phthalocyanine, Zinc-Phthalocyanine, Nickel-Phthalocyanine,Magnesium-Phthalocyanine and other metals associated with thePhthalocyanine.

A thick film may be made of the organic materials disclosed herein, theorganometallic materials disclosed herein, or a combination thereof. Theterms organic, organometallic, and any combination thereof may be usedinterchangeably in these descriptions. In at least one embodiment, athick film does not contain diluting agents or additives such as otherhigh-K dielectrics, or semiconductors. Additives can be used for thepurpose of dilution of a pure film to reduce the film potency in termsof charge storage but also beneficially increase resistance. Additivescan be both organic and inorganic in nature. Additives can have aparticle size, for example, of 50 nanometer or higher.

The fabrication of the novel thick film dielectric can be effectuated invarious manners, one of which comprises first forming an organic vehicleby mixing a resin and a solvent and then adding a mixture of a solventsystem with an organometallic material such as copper Phthalocyanine,for example, followed by a heat treatment to ensure the uniformity ofthe mix. The green paste can be improved by further mulling and or rollmilling and subsequently applied to form a thick film on an electrode.The thick film is then dried for solvent removal and optionally heatedto slightly elevated temperatures to promote the formation of neckingbetween the various particulates to trigger the onset of sintering andto form a thick film with a continuous phase or a substantiallycontinuous phase of compacted metal-phthalocyanine particulates. Thethermal energy required may be estimated to correspond to at least a onetenth of the melting point, and may correspond to as much as one half ofthe melting point, of the organic and/or organometallic material. Thevehicle material is formed by mixing a dielectric resin and solventsunder heat to form a paste.

The formation of a diluted film can be effectuated in various manners,one of which may include mixing a dielectric material with the novelorganic, or the novel organometallic or a mixture of the novel organicto the novel organometallic materials at advantageous ratios orconcentrations, followed by a heat treatment to enhance the mixing, thento print on an electrode, then to heat and the particulate in the thickfilm to densify the particulate through the onset of sintering and toform a film having a substantially continuous phase within which adispersed additive dielectric additive is in discrete phase or noncontinuous phase. The thermal energy required is estimated for drying isbetween 60 C and 80 C and the temperature required for densification isin the 150 C range which is typically at least one tenth of the meltingpoint, and in one or more embodiments, one half of the melting point, ofthe organic and/or organometallic. In some cases, the organic and/ororganometallic materials are semiconductors.

Dielectric material additives may be, but are not so limited to,alumina, silica, aluminosilicates, alkali aluminosilicates, alkalinealuminosilicates, Zeolites or an organic such as Bismaleimide-Triazine,cyanate ester, epoxy, silicones, polystyrenes, ethyl cellulose,nitrocellulose, Si, ZnS, GaAs, BaTiO3 or a combination thereof.

The net charge storage of a film can be optimized by changing theproperties of the raw chemical ingredients used in a mixture as well asby changing the process parameters used during fabrication.

For instance, optimization techniques in the materials preparation mayinclude, but are not limited to, changing the ratio or concentration oforganic to organometallic materials used to form the film, or changingthe concentrations of additive dielectric materials with respect to thenovel organic material used in the novel dielectric paste that is priorto applying the dielectric thick film to the electrodes of a capacitor.Another method entails changing the dielectric constant of a dielectricmaterial by choosing a material with a characteristic dielectricconstant that is higher or lower that one used before.

Yet another technique includes doping special organometallic materialswith chemicals that can deliver metallic dopants able to interact withthe organometallic materials and lead to an observable overall dilutionin charge storage capability. Such metallic doping methods may result inless efficient charge-storing dielectric layers but can also minimizecharge storage.

For instance, optimization techniques in the process category maycomprise, but are not limited to, controlling the thickness of adeposited layer, which may be a near pure film or diluted film, orcontrolling the stepped thermal profiles for heating the materials. Theheating and cooling profiles can lead to formation of crystalline phasesin the substantially continuous phase of the organic, organometallic, ormixed organic to organometallic materials. Other optimization methodsinclude applying a high intensity electric field for aligning themolecules of the organometallic materials in special orientations.

The stabilization of the one or more capacitors disclosed herein madefrom the ultra-high charge capacity dielectric material(UHCC-dielectric) is accomplished through multi-layering or the use ofvarious layers. Each layer can be tuned to have more or less chargestorage capability from a maximum charge storage layer (being the purefilm) to a low charge storage capability layer (having diluents ordielectric additives, or semiconductor additives or metal dopants). Theadditives play a key role in increasing internal resistance of the noveldielectric which in turns minimizes leakage currents.

Further stabilization of the novel dielectric used to construct thesuper capacitor is accomplished in the electrode region by having aninterface layer between the electrode and the multilayer dielectric. Theinterface layer is configured to behave similar to a diode therebyallowing the passage of current substantially in one direction. Theinterface material can be derived by choosing a suitable metal dopingfor a specific organometallic. For example, Silver if the preferredmetal dopant when the special organometallic is copper phthalocyanine.

Yet another method for stabilization in the electrode region is based onthe use of a thin film having suitable electrical properties formaximizing the electrical coupling between the dielectric and theelectrode. This thin film interface can be obtained by applying a liquidcontaining the appropriate carbon, activated carbon or graphene andsubsequently evaporating the liquid to leave the residual dopants on theelectrode interface and therefore form an interface layer bridging thedielectric material with the electrode. The concentration of chargecarriers and pore size at the interface is tailored to avoid leakagecurrents and maximize surface area at the electrode level. The liquidinterface can have various degrees of polarity and heavy ionicconcentration.

The one or more dielectrics, capacitors, and related methods disclosedherein make use of substantially continuous phases rather than dispersedor discrete phases of the special organic and organometallic materials.This may be counter intuitive to the practiced state-of-the-art. Forexample, US Patent Publication No. 2006/0256503 A1 by Kato et. aldiscloses the use of organometallic materials in a dispersedconfiguration and for high frequency with limited high storagecapability (below 150 degree C.). The present invention uses the routeof liquid based chemistry to promote the densification of the copperphthalocyanine and zinc phthalocyanine particulates and the overallbehavior of the novel capacitor depends on the thickness and the qualityof the film which is related to the densification achieved between theparticulates. This is exactly opposite from the teaching of Kato et. al.This is also different than all the thin film deposition techniques(sputtering and vapor phase deposition to name two) that inhibits chargebuild up.

Furthermore, the use of dispersed phases, which is conventionally used,is obtained through using high charge storage materials as fillers.Special care is given to avoid short circuiting the dispersed phases.Furthermore, special care needs to be taken to avoid dielectricbreakdown taking place between the dispersed phases. Also, the use ofhigh charge storage materials as fillers in a high frequency regimeinherently limits the storage capability of the composited materials.The present invention is diametrically opposite in regards to someconventional practices. By using layered materials and using specialorganic and organometallic materials having delocalized electrons at themolecular level and having a long dielectric relaxation time, chargescan be stored to a much higher extent without dielectric breakdown andwithout short-circuiting across the material.

The one or more UHCC-dielectric materials disclosed herein arestabilized to enable a super-capacitor having a macroscopic ultra-highcharge storage with dielectric constant far exceeding 2,000 reachinginto the 100,000 range and in one or more experiments, (post furtherstabilization) in the 35,000,000 range and higher.

The ultra high energy storage capability achieved in the one or moreexperiments relating to the disclosed subject matter enables far rangingapplications from personal digital assistants, computers, renewableenergy storage, energy transport, automotive electric cars and hybrids,and other applications to name a few.

The one or more capacitors and dielectric materials described herein arerelevant from an industrial stand point and applicable to variousbattery related use.

Copper phthalocyanine is among the best known and best performingblue/green color pigments in inks and paints. It is colorfast and veryintense, making it widely used. It has been in use for about 80 yearssince its development as a pigment by Dupont®.

Another property of copper phthalocyanine is its extremely highdielectric constant, making it orders of magnitude higher than thehighest K ceramics used in electronic applications. It is unusable inelectronic applications, however, because of the extremely lowfrequencies at which it has the high dielectric constant. Recently,however, speculation about supercapacitors use as battery replacementshas raised the possibility that copper phthalocyanine could be used forsupercapacitor applications. At frequencies from about 10 hz and below,the dielectric constant and hence capacitance are dramatically higher,giving supercapacitors using copper phthalocyanine much greater powerstorage capability than the best batteries currently available.Calculations based on simple estimates indicate a power storagecapability in copper phthalocyanine capacitors of one to two orders ofmagnitude greater than a fuel tank of similar volume and weight, givinga possible range of up to many thousands of miles between charges.

These capacitors also have the potential of being much more efficientdevices for storing and transporting energy in general than fossil fuelscould ever be, affording the potential of revolutionizing the way energyis transported and stored. For example, a single freight train could becapable of transporting the energy equivalent of several million barrelsof crude oil, as much as several tanker loads of crude oil. Thistechnology could supersede the use of hydrogen-powered fuel cells inautomobiles. They also make practical the use of nuclear power to chargethese devices and transport the power in directly usable form toautomobiles without the need for chemical conversion to a fuel such ashydrogen.

Use of Phthalocyanine in Capacitors

The United States published patent application no. US2006/0256503 to Ikiet al. discusses a novel use of various materials including copperphthalocyanine. The application intended by Iki et al. demands verydifferent properties from the one or more devices, methods, and otherembodiments described herein. In Iki et al., the frequency range and thedielectric constant is in the range of 150. This dielectric constant ismuch lower than the intended use. One particular technical aspect thatwas described in the referenced patent emphasizes a major problemimpeding the development of the ultimate high dielectric constant fromthe copper pthalocyanine and that is, the semiconductor property of thematerial. Iki et al. chose to use the material in a finely dividedstate, diluting it so that no conductive pathways are developed betweenthe capacitor plates.

The one or more capacitors and devices disclosed herein overcome thesemi-conductive nature of the material and make use of copperpthalocyanine in a constructive way to promote the build of much higherK of tens to hundreds of thousand by doping one of theelectrode/capacitor interfaces to form a diode junction at that point.The leakage reduction is achieved using this method. Furthermore thedevice becomes less sensitive to the thickness of the dielectric layer.Yet another approach is to use a thicker layer of the copperpthalocyanine to increase resistance. This method is used along withstabilizing the innerlayers and minimizing voltage breakdown. Based ontheoretical understanding and literature reviews, the Copperphthalocyanine has a crystalline configuration that consists ofmolecules stacked flat against each other. This may suggest that theinteraction between the copper atoms in the center of individualmolecules and neighboring phthalocyanine molecules is the origin of theextremely high dielectric constants observed in the one or more devicesdisclosed herein. The phthalocyanine molecule has a system of sixteendelocalized electrons. Since systems of delocalized electrons obey therule 6+4n, where the numbers represent electrons and n is an integer,systems containing 6 electrons (benzene), 10 electrons, (naphthalene),14 (polycyclic aromatic molecules), and up in increments of 4 electrons,this yields stable configurations.

Phthalocyanine may be converted to an anion by deprotonating twonitrogens in the ring, achieving the stable 18 electron configuration.The center of the molecule is suitable for containing a divalent cationsuch as copper. An extremely stable organic anion is thus achieved.

Since the CuPc molecules are stacked flat, placing copper ions inindividual molecules close enough to interact with their neighbors,conductivity related to movement of the cations through a “tunnel” ofnegative Pc rings of nitrogen might be expected, and does occur. Thecations are apparently easily moved in an electric field so as topolarize large numbers of adjacent molecules simultaneously. Thepolarization in addition to polarizing molecules producing extremelyhigh dielectric charge capacity, causes the copper ions to movesufficiently that some transfer of copper cations from molecule tomolecule through a sort of “tunnel” of electric charge from the Pc ionswill occur. This causes the phenomenon of low insulation resistance thatwe see in our compositions, in addition to extremely large chargecapacity in our capacitors.

Mixtures of different sizes of crystallites as well as different metalsin the center of Pc anions hinders movement of cations betweencrystallites in the one or more dielectric materials and compositionsdisclosed herein. Pure CuPc has a resistivity as low as 8 Kohms per milof thickness per cm sq. in our films. By mixing different MPccrystallites (M=Cu and Zn), and adding BaTiO3 to the compositions. Theresistance may be increased to about 1 Mohm per cm square. Furtherincrease of several orders of magnitude in resistance can be achieved bythe use of thick (as high as hundreds of mils) dielectric films. Theadvantageous nonlinearity of charge versus voltage makes this possible.

Supercapacitors

An alternative to the chemical battery is the so-called supercapacitor,which does not generate electrical current by a chemical reaction, butsimply stores an electrical charge by the electrostatic attractionbetween oppositely charged plates. The amount of charge stored oncapacitor plates is enhanced by interposing a layer of material with ahigher dielectric constant between the plates. These materials can makethe amount of charge stored tens of thousands of times greater than whenthe intervening space between capacitor plates is air or a vacuum. Thereis a need for a supercapacitor that is competitive with lithium ionbatteries.

Dielectric Materials

The dielectric behavior of a material depends on its short-rangeelectrical conductivity. The short-range motion of a material's chargecarriers leads to electrical energy storage. The capacitance, C (in F orC/V) of a dielectric material is defined as the ratio of the storedcharges, Q (in Coulombs-(C)), to the applied voltage V (in Volts):C=Q/V

The ratio of the capacitance of a condenser filled with a dielectricmaterial, C, to that of a vacuum capacitor, Co, of the same geometry(spherical, cylindrical, parallel plate) is defined as the dielectricconstant of that material:k=C/C ₀

For a parallel plate capacitor with an area A (in m2) and separated bydistance, d, (in meters), C and C₀ are found to beC0=∈₀ A/dC=∈A/d

where ∈₀ is the permittivity of free space (8.854×10−12 C2/m2 or F/m)and ∈ is the permittivity of the dielectric material (F/m). The relativedielectric constant of the material is therefore the ratio of thematerial's permittivity, ∈, to the permittivity of free space ∈0:k*=∈/∈0

The relative dielectric constant (also referred to as the relativepermittivity), which is independent of the applied electric field at lowfield strengths. For very strong fields, the permittivity may depend onthe field strength and saturation effects are detectable.

The dielectric constants of materials are frequency dependent and can beas low as 3.78, for materials such as SiO2, and very high, about 1100GHz, as with materials such as BaTiO3. Since the relative dielectricconstant of a dielectric material is greater than unity, the ability ofa condenser to store charges is increased. The reason for this increasein capacitance is a result of polarization effects occurring at themolecular level inside the material. The charged species inside thematerial are displaced from their equilibrium position and createdipoles under the influence of an externally applied electric field. Thecreated dipoles tend to orient with the electric field and tie upcharges on the plates of the condenser. Consequently, part of theapplied electric field is neutralized. Indeed, if the voltage across adielectric field condenser is expressed as a function of the vacuumcapacitance, the following expression results:V=(Q/k)/C0

The voltage required to maintain the same surface charge is only afraction of the voltage across the vacuum capacitance. The bound chargeis neutralized by the polarization of the dielectric. The charge whichis not neutralized by the dipoles is called the free charge and is equalto Q/k. The free charge sets up an electric field and voltage toward theoutside.

There are four major polarization mechanisms in dielectric materialsthat contribute to charge storage, all of which involve short-rangecharge motion. Depending on the operating frequency, one or acombination of several polarization mechanisms might be at work.

Electrical-Double-Layer Capacitors, Super-Capacitors, andUltra-Capacitors

Simple air-gap capacitors consist of two parallel or concentricelectrodes which are made up of an electron-conducting material,connected to an external circuit. The electron conducting material canbe any good electronic-conducting material, well-known to thosepracticed in the art, such as copper, silver or gold. The two oppositeplates are charged with opposite charges (electrons on one plate andelectrical holes on the other plate). These charges balance each otherand if the space between the plates is filled with air (e.g. and air-gapcapacitor) the energy that can be stored by the device (U) is given bythe equation:U=½CV ²

where C equals the capacitance of the capacitor and V equals the appliedvoltage.

The capacitor electrodes need to be in close proximity to each other inorder to generate a high capacitance, and they can be parallel flatplates, or concentric cylinders or spheres, or any desired shape thatcan hold charge of opposite sign in close proximity to each other.

For parallel-flat-plate capacitors, the capacitance (C) is given by theequation:C=∈ ₀ A/d

where A is the area of the plates, d is the separation between theplates and ∈₀ is the dielectric permittivity of free space or air whichis nearly the same.

In order to increase the amount of energy that can be stored in acapacitor, electrical configurations are developed in which the spacebetween the electrodes is replaced by a material that exhibits a largerdielectric permittivity.

As charge builds up on the electrodes, and equal and opposite chargebuilds up on the dielectric filling the space between. The dielectricpermittivity of the space between the electrodes increases to adielectric permittivity (∈) value of:∈=κ∈₀

where κ is the dielectric constant of the material between theelectrodes.

The stored energy is proportional to the capacitance, and thecapacitance increases proportionally with increased permittivity andelectrode area.

The maximum operating voltage is determined as either the dielectricbreakdown voltage of the material between the electrodes, or itsdecomposition voltage. Most are limited to about two (2) to about three(3) volts.

Super-capacitors and ultra-capacitors are designed to exhibit very highvalues of capacitance in order to have the ability to store a largeamount of charge. There are at least two common ways to achieve this byeither increasing the surface area of the electrodes and/or increasingthe dielectric constant of the materials between the electrodes.

There are many inventions relating to electrode materials forsupercapacitors. Commercial electrodes and capacitors (Maxwell, Ness,Nippon, Power Systems, Batscap, LS Cable and others) are made fromcarbon (graphite) powder or activated carbon powder. Powder increasesthe surface area of the electrodes over a solid electrode by many times.New developments are ongoing in graphene materials, carbon nanorods ornanotubes and porous materials to increase both the surface area andconductivity of the electrodes. Some studies have also examinednanoporous metals, metal oxides and semiconductors.

Portions of the subject matter disclosed herein concern increasing thedielectric constant of the materials between the electrodes. When thismaterial allows diffusion of ionic species of different sign of chargeto cause the polarization that enhances charge build up, then it iscalled an electrolyte. Electrolytes can be liquids, fluids and solid.Typical electrolytes used in super- or ultra-capacitors include aqueousacids, organic and ionic liquid electrolytes. (sulfuric acid orpotassium hydroxide in an aqueous solution, propylene carbonate, TEABF₄in acetonitrile, BMIIM, EMI-BF₄ which is1-ethyl-3-methylimidazolium-tetrafluoroborate, and EMI-DCA).

Frequency Dependence of Polarization

Since the polarization of matter is of interest, it is desirable toclassify the various types of polarization with reference to the timerequired for the polarization process. The polarization process alwaysinvolves rapidly forming dipoles and in some instances may also involveslowly forming dipoles (referenced in its entirety is a 1994, PhDdissertation on Surface Modification Of Sodium Aluminosilicate glassesUsing Microwave Energy by Z. Fathi)

Electronic polarization is a result of the displacement of the electronsin the atoms relative to the positively charged nuclei. This processrequires about 10⁻¹⁵ seconds and corresponds to approximately to thefrequency of ultraviolet light. Moreover, this process gives rise to aresonance peak in the optical range. The refractive index of a materialis strongly dependent on the electronic polarization.

A relatively small atomic polarization arises from the displacement ofatoms relative to one another inside the molecule, a process requiringabout 10⁻¹² to 10⁻¹⁴ seconds and corresponding to the frequency ofinfrared light. In ionic crystals, a similar but usually largerpolarization arises from the displacement of oppositely charged ions, aprocess requiring about 10⁻¹², and corresponding to the frequency of thefar infrared region. A resonance absorption occurs at a frequencycharacteristic of the bond strength between the ions. Resonanceabsorption is characterized by large restoring forces and small dampingeffects.

Orientation polarization, also referred to as dipolar polarization,involves the perturbation of the thermal motion of ionic or moleculardipoles, producing a net dipolar orientation under the direction of anapplied electric field. This is perhaps the most important mechanism ofpolarization in the microwave frequency range.

The time required for the dipolar polarization process depends upon thefrictional resistance of the medium to the change of molecularorientation. The resistance to dipolar motion is equivalent to largedamping effects, resulting in relaxation type absorption. For gases, thetime required for the process is in the range of between about 10⁻¹²seconds, corresponding to the far infrared region. For small moleculesin liquids of low viscosity, the time required is between about 10⁻¹¹.For large molecules or viscous liquids, the time required is in theorder of 10⁻⁶ seconds, corresponding to radio frequencies. The highinternal frictional resistance of very viscous liquids, glasses, andsolids may lengthen the time required for the polarization process toseconds, minutes, or longer.

The orientation polarization mechanisms can be categorized in two types.First, molecules (liquids, gases and polar solids) containing apermanent dipole may be rotated against an elastic restoring force aboutan equilibrium position. The time required for the oscillation of thesepermanent dipoles is in the order of 10⁻¹⁰ to 10⁻¹² seconds at roomtemperature. The orientation polarization involving permanent dipoles issometimes referred to as deformation polarization.

The second mechanism of dipolar polarization involves the rotation ofdipoles between equivalent equilibrium positions. This mechanism is ofspecial interest in glass and ceramic materials. The interstitialcations give rise to losses, which are greater the more loosely boundthe cations. The required time for this process is greatly dependent onthe structure of the inorganic or organic matrices, and the bindingenergy distribution of the alkali ions. Due to the appreciable atomicdistances involved in the ionic transitions, this polarization occurs ata frequency range of 103-106 Hz, at room temperature. Because thismechanism involves the same mobile cations that contribute to the dcconductivity, it is also referred to as migration loss.

In heterogeneous materials, an additional type of polarization,interfacial polarization, arises from the accumulation of charge at theinterfaces between phases. It arises only when two phases differ fromeach other in dielectric constant and conductivity. For a two-layerdielectric, when the product of the dielectric constant ∈1 of one phaseand the conductivity σ2 of the second phase is unequal to the product ofthe dielectric constant ∈2 of the second phase and the conductivity σ1of the first phase, that is, ∈1 σ2≠∈2 σ1, space charge polarization isexhibited. Impurities or second phases usually represent physicalbarriers to conduction and lead to charge build up at the interfaces ofthe heterogenous materials. The charge pile-up at the different barriersleads to localized polarization of the material. If the ac field is oflow enough frequency, a net oscillation of charge is observed. Theinterfacial polarization is observed over a broad range of frequencies.

The losses associated with the different polarization mechanisms occurat different frequency ranges. The atomic and electronic polarizationsusually result in resonance absorption peaks. Orientation and spacecharge polarization on the other hand, results in relaxation absorption.In practice, depending on the material, the orientation and space chargelosses can be quite broad and extend over an overlapping range offrequencies. It is often impossible to distinguish between them.

Of all the possible losses, orientation polarization is probably thedominant loss mechanism in the RF and microwave frequency range.However, along with orientation polarization losses, Maxwell-Wagnerpolarization together with DC conductivity losses are importantcontributions to charge storage and the loss mechanisms associated withthem. Hence the complex nature of the dielectric constant

There are two ways in which the complex nature of the dielectricconstant is demonstrated: a) Ampere's circuital law and b) chargingcurrent in a linear dielectric within a circuit configuration. Thefollowing is limited to the charging current within a dielectric.

The stored charge in the dielectric can be expressed as a function ofthe applied voltage and the capacitance (a constant):Q=V/C

The charging current can be expressed as:Ic=dQ/dt

Combining the two equations gives:Ic=C(dV/dt)

For a sinusoidal voltage in the form of V=V0exp(iωt), the expression forthe charging current is as follows:Ic=iωCV0exp[i(ωt)]

In an ideal dielectric there would be no free-ion conduction and no losscurrents. The total current would therefore be equal to the chargingcurrent, Ic, and would lead the voltage by 90 degrees In realdielectrics (actual insulating materials), there are loss currentsarising from two sources: a) ohmic conduction and b) polarization. Theohmic conduction losses involve the long range motion of chargecarriers. Polarization (previously discussed) results in losses due tothe dipoles resistance to oscillation and/or rotation under analternating field. The ohmic and polarization loss currents can beexpressed as:I _(O) =G _(dc) VI _(P) =G _(ac) V

in which Gdc and Gac are the dc and ac conductance in units of ohm-1.The loss current, I_(L), corresponds to the summation of both the ohmicloss current, I_(O), and the polarization loss current IP:I _(L) =I _(O) +I _(P)

Expressed as a function of voltage and conductance, IL becomes:I _(L)=(G _(dc) +G _(ac))V

The loss current is in phase with the applied voltage because Gac andGdc are not complex in nature. The total current of the capacitor filledwith a dielectric corresponds to the summation of the charging currentand the loss current:I _(T) =I _(C) +I _(L)=(iωC+Gdc+Gac)V

The charge stored in the dielectric can be expressed asQ=CV=kC ₀ V

Since the total flow of current is equal to the variation of charge withrespect to time, the following expression is obtained:I _(T) =dQ/dt=C dV/dt=kC ₀ iωVkC ₀ iωV=(iωC+G _(ds) +G _(ac))V

this expression yields:k=C/C0−[i(Gdc+Gac)]/ωC ₀

Thus, one demonstrates the complex nature of the dielectric constant ofthe material. The real and imaginary parts of k* are given as:K′=C/C0 and k″=(Gdc+Gac)/ωC ₀

The total current inside a real dielectric possessing both charging andloss processes is expressed as a function of one complex parameter, k*,that is intrinsic to the material and has the following forms:k*=k′−ik′

The permittivity of real dielectrics is also complex in nature:∈*=∈′−i∈″

and is related to the complex dielectric constant:k*=∈*/∈ ₀

The real part of k*, k′, describes the ability of the dielectric tostore charges and is referred to as the charging constant or dielectricconstant. The imaginary part of k*, k′, describes the losses exhibitedby the dielectric and is called the dielectric loss factor. The ratio ofthe loss factor to the dielectric constant, tan δ, is referred to as theloss angle or the dissipation factor. The loss tangent is defined alsoas the ratio of the loss current to the charging current:

It is useful to relate the relative dielectric constant, k′, of thematerial, which is a macroscopic characteristic of the material, and thepolarizability which is a characteristic of the molecule. Thisrelationship can be established by considering the total electricdisplacement field or the electric induction, D (in C−m2). In freespace, the relationship between the induction and the electric field isgiven by:D=∈ ₀ E

In the presence of a material, the electric induction is a function ofthe properties of the medium, and is related to the externally imposedelectric field by the complex permittivity of the material, ∈*, throughthe following expression:D=∈*E

The electric displacement field is also defined as the sum of theinduction (if there was no dielectric in the condenser) and thepolarization field within the material:D=∈ ₀ E+P or P=D−∈ ₀ E

Therefore, we can express P as a function of E:P=∈*E−∈ ₀ E=(∈*−∈₀)E=∈ ₀(k*−1)Ek*−1=P/(∈₀ E)

the definition of the polarization which is described as the totaldipole moment induced in a unit volume of the material. The polarizationis a measure of the change in the capacitance (or field), so that:P=(C−C0)V=C0V(k*−1)=(Q/V)V(k*−1)P=∈ ₀(V/d)(k*−1)P=∈ ₀ E(k*−1)

The tan δ, the ratio of the loss factor to the dielectric constant istherefore:tan δ=∈″/∈′=(∈s−∈inf)ωτ/(∈s+∈sw2τ2)

Space Charge Polarization Versus Loss

There are two main types of interfacial polarization. The first involvesa variation of electrode polarization, the second consists of thedielectric behavior due to heterogeneities in materials (Maxwell-Wagnerpolarization)

Conductivity Losses

In mixtures containing large amounts of conductive phases, high lossesdue to dc conductivity can occur. The conductivity losses can berepresented by:E″dc=σdc/ω∈ the conductivity losses dominate at low frequencies.

Examples:

EXAMPLES

Paste Preparation.

There are several approaches to preparing films with which to makecapacitors. Considerable work has been done on thin films of copperpthalocyanine which were prepared by sputtering or evaporation. Thereare several problems with using thin films, among which are a lowbreakdown voltage due to the thinness of films, and limited ability tomake composite films.

One or more investigations disclosed herein investigated thick filmstructures with pthalocyanine, therefore, and began investigatingmethods of making films that would act as capacitors. First attemptswere to use commercially available copper pthalocyanine made by the sameprocess as pigmentary copper pthalocyanine (CuPT), which was about 2000Angstroms particle size. Two problems arose: first, the solids loadingof potential thick films was only about 30 weight percent, or 21 volumepercent. TABLE I illustrates the composition of polymer containing thickfilm CuPC compositions.

TABLE I Weight Chemical Percentage CuPC (2000 28% Angstrom) Texanol 69%Ethyl Cellulose (Dow)  3%

The CuPC was dispersed by mulling the above mixture between two glassplates until a satisfactory dispersion was achieved, as determined bydrawdown examination under a microscope. This paste was applied byscreen printing, and extensive mesh defects and mud cracking made thefilms impractical.

Another approach was tried, this time using only solvent and CuPC. TABLEII illustrates Solvent/Slurry of CuPC/Texanol.

TABLE II Weight Chemical Percentage CuPC 33% Texanol 67%

This material was again dispersed by mulling between two flat glassplates, then instead of screen printing the material was skived on byusing a spacer tape on the edge of substrates and drawing down the inkslurry using polyimide tapes with 60 micron thickness along the edges ofthe film, and an Exacto knife blade as a drawdown straight edge. Again,excessive cracking was observed when films were dried at hightemperatures, which was countered by drying films very slowly; undervacuum for example, the solvent was removed at about 55 degrees C.Cracking was dramatically reduced using this technique.

Gold plated Kovar(r) substrates 17×17 mm in size were obtained and usedas printing substrates/electrodes. These were coated with CuPC at about20 microns volume thickness after drying, assuming no voids; in actualpractice, about 25 to 30 microns were measured. Capacitors were thenmade by clamping two substrates with CuPC films facing together with aC-clamp, and optionally heating overnight in an oven at 80 to 150degrees C.

Electrical properties of these films were then measured and we foundthat the internal resistance of these capacitors was measured as high as15,000 ohms, with capacitance in excess of 50 microfarads, on s 2.5 sqcm capacitor. Thus, the dielectric constant was initially determined tobe in excess of 500,000.

Capacitors were also successfully made by drawing down CuPC slurry onaluminum foil, but these foil based devices were more difficult tohandle and prepare than the ones on the thicker gold plated Kovar.

CuPC Film Densification

The CuPC films readily sinter and densify at 80 degrees C. and above,due to the extremely fine particle size of the powder (around 2000angstroms). An oxygen free atmosphere is desirable because in oxygen theCuPC oxidizes, and the oxide film coating gives the film a lowerinsulation resistance. The reduction in electrical resistance by thisoxide layer is about 90 percent, although capacitance is doubled.

We have found that heating at 80 degrees C. reduces the tendency tooxidize and dramatically reduces the tendency of cracks to form in theCuPC film during drying. TABLE III illustrates some Early Test Resultsfrom Devices Made in Above Experiments.

TABLE III Temperature Pressure Pressure Shear Thermal During DuringMeasurements Shear Method Treatment Process Measurement ResistivityCapacitance Screen Printing Glass Plate + Metal Blade 250 C. to 311 C. NN 40 MOHMs ++ <0.4 nF Skiving on 2 Glass Plates 150 C. Y Y 14KOHMs/Cm2 >40 mcrF Metal Foils Skiving on 3 Glass Plates 150 C. Y Y 5KOHMS/Cm2 >40 mcrF Bottom Electrode Dip Transfer No Shear 150 C. Y Y 40MOHMs ++ <0.2 nF

Using Additives in CuPC Films Zinc Pthalocyanine

Zinc Pthalocyanine (ZnPC) was investigated as an additive to potentiallyincrease insulation resistance (IR) of CuPC films. ZnPC was dispersed ina slurry containing Texanol(r) (See Table IV) to use in a mixture withCuPC slurry, to see whether the IR of capacitors made from thesemixtures could be increased. TABLE IV illustrates a formula of slurrycontaining ZnPC.

TABLE IV Weight Chemical Percentag Zinc 33% Pthaloccyanine Texanol 67%

A 10/90 mixture of the composition in Table IV (ZnPC)/Table II (CuPC)was made and films were drawn down on aluminum foil and Kovarsubstrates. The 10% ZnPC doped films were joined to 100% CuPC films onaluminum foil and Kovar substrates. Resistances in the megohm range weremeasured with these devices, and over 40 microfarads capacitance wasmeasured.

Adding Glycerol to Reduce Shrinkage and Improve Insulation Resistance

We have found that use of polar solvents improves electrical propertiesof CuPC films in these capacitors. CuPC films sintered at 150 C. forexample, can be difficult to join effectively when two coated electrodesare abutted and pressed together. One typically can get high resistancein the megohm range and extremely low capacitance, around 0.1 nanofaradsper square centimeter.

This difficulty can be overcome by adding about 10 percent by volume ofglycerol to the CuPC in the slurry. The Texanol solvent can be easilydried while leaving the glycerol behind. Insulation resistances of 200to 250 Kohms are typical, capacitance approaching 1 millifarad/cm2 isobtained, yielding a dielectric constant as high as 35,000,000. Table Vgives typical formulations for compositions with these additives. TableVI gives the electrical properties of capacitors with glycerol additive.

Other polar solvents, notably acetone and methanol, have the same effectwhen allowed to diffuse into the films from the edges, but theseexamples are too volatile to be practical as additives. The reason whyglycerol and these solvents are effective is probably that there is someplasticization of surface diffusion of solvents into the microcrystalsof CuPC. This permits the two layers to form an intimate interface, andfacilitates their joining to produce an electrically functional film.TABLE V illustrates formulations of CuPC and ZnPC/CuPC slurries.

TABLE V Weight Chemical Percentage Formulation 1 CuPC 33.0% Glycerol 3.0% Texanol 64.0% Formulation 2 CuPC 29.4% ZnPC  3.6% Glycerol  3.0%Texanol 64.0%

TABLE VI illustrates electrical results of tests of glycerol containingfilms. As can be seen, the addition of glycerol made a significantdifference.

TABLE VI Device Built ROHM 1st Half 2nd half CPC ZnPC TXN TPG Glycerol Cand tested C (F) (24 hrs) sec sec 21% 7% 69% 3% B12/B12 4.0E−05 120 1080(2 caps in series) B9/B10b 1.3E−05 1.0E+07 12 108 (10 cm × 1 cm) 33% 67%B9 1.3E−05 7.0E+06 30 210 B11/B10b 4.0E−05 1.8E+06 2 120 (10 cm × 1 cm)B11 4.0E−05 1.6E+06 3 27 33% 67% B6/B6 4.0E−05 1.2E+06 B11/B10b +2.5E−06 8.0E+06 B field B82/B82 3.5E−07 4.0E+07

Applying Pressure During Heat Treatment (Drying and Partialdensification or Partial SINTERING)

The CuPC and ZnPC. being finely divided, will sinter at temperaturesapproximately one half their melting point (in degrees Kelvin). In fact,because of the submicron size of the CuPC, it can be expected to sinterat well below half its melting point (603 degrees C.). We have beensuccessful in densifying the CuPC at about 80 degrees C., and haveobtained high capacitance (as high as 35,000,000) using temperatures of80 to 150 degrees C. and adding low to moderate pressure by squeezingthe film with a vise. The use of a glycerol or other additive,preferably with low solubility capacity for CuPC, also aids in thecoalescence of the CuPC into a solid body at lower temperatures andpressures.

In one or more experiments, it was demonstrated the formation of amonolithic structure by successive heating, first as low as 60 degreesC., then increasing the temperature to 150 degrees C. Thus, it ispossible to create highly dense thick films of CuPC, which is aprerequisite to forming high dielectric constant dielectric material.

Multiple Solvents

Often, when a very low solids slurry is to be printed, the use ofseveral solvents is helpful in getting the required degree of shrinkagewithout causing mud cracks. If a single solvent dries rapidly in such aslurry there is not sufficient force generated as solvent evaporates tocause the particles to pack tightly together. However, if theevaporation is staged so that in a first stage the particles are forcedcloser together while still in a liquid matrix, less shrinkage must beundergone in subsequent solvent evaporation, and the particles are morelikely to shrink uniformly. Also, the addition of a limited amount of avery viscous, very low vapor pressure solvent was the last to dry willdramatically reduce the rate of drying and also provide viscous force tocause the particles to interact with each other, dramatically reducingthe occurrence of film defects. A final solvent with a limitedsolubility in the slurry solids also helps the particles to coalesceslowly, as though the final body had been plasticized. Once a solid bodyhas been achieved, the last component of the solvent system can beevaporated, leaving a solid body. A three-component solvent system thatwe have evaluated with success is listed in Table VII. The glycerol wascalculated to provide about 10% by volume of the CuPC and/or ZnPC solidsin the slurry. Glycerol is very slow drying compared to texanol andtripropylene glycol, so it is essentially all present as the lastremaining component. If desired, the Glycerol can be left in thedielectric body without harming capacitance, and actually improving theinsulation resistance. Sealing the edges of the capacitor will make theglycerol essentially permanent. TABLE VII illustrates a three-componentsolvent system investigation and results.

TABLE VII Weight Chemical Percentage Texanol 66.0% Tripropylene glycol29.5% Glycerol  4.5%

Graded Particle Size Mixtures in Improve Solids Packing, Reduce FilmDefects

Often, to improve solids packing in a film, a slurry makes use of thephenomenon of graded particle sizes in the slurry. This permits smallerparticles to fit into the spaces between the larger particles, thuspermitting higher solids loading in the slurry and reducing the amountof shrinkage during drying to densify the film.

Usually, the best results are obtained using three graded particlesizes, each about one fourth the size of the next larger particle size,and in about one fourth the volume of the next larger size. Two particlesizes leaves significant unfilled space that could be taken up by asmall fraction, and more than three particle sizes adds very little moreto the packing level. A typical mixture of particle sizes and theirrelative volumes is illustrated in Table VIII.

TABLE VIII Percentage Particle Size By Weight 5 microns 75.0% 1.25microns 19.0% 0.33 microns  5.5%

Carbon as an Interface; Using Mesh as at Least One Electrode

CuPC does not develop entirely satisfactory adhesion to metal surfaces.One solution to this problem is the use of a carbon interface thatdevelops better adhesion both to the metal electrode and to the CuPC orZnPC layers. This approach also has the advantage of providing increasedsurface area for the electrode, enhancing the capacitance. This raisesthe possibility of using a metal mesh electrode to allow drying ofcapacitors after electrodes have been applied, after which a carboninterface is applied over the mesh. The resistance at the interfacebetween CuPC or ZnPC/CuPC layers is also improved by the addition of acarbon layer between the pthalocyanine containing layers. The decay timedue to internal resistance is lengthened. In fact, the films on which weobtained a 35,000,000 dielectric constant all used carbon electrodes asan interface between Kovar electrodes and the CuPC/ZnPC films.

Curing Films Under Electrical and Magnetic Fields

Electric and magnetic fields have a major effect on the electricalproperties of CuPC and ZnPC and mixtures in capacitors. We have foundthat an electric field significantly increases both capacitance andinternal resistance of the capacitor, whereas the magnetic field causesan apparent increase in capacitance but a decrease in resistance. Thisinvites speculation as to whether joining two films, one electricallybiased and the other cured under a magnetic field. There is significantliterature about the effect of electrical fields on electricalproperties of CuPC, but less literature treating the effect of amagnetic field on these properties.

A strong (3000V) AC electrical field was applied to capacitors, withstrong but varying results on capacitance and resistance. A 23.4 volt DCfield was used with more predictable effect, yielding both improvedinternal resistance and capacitance. Biasing at 60 degrees C.temperature improved the half life of the capacitor markedly. Biasing at−40 degrees C., then warming to room temperature and then measuring thevoltage decay when bias was removed gave the most improvement in voltagedecay times.

TABLE IX C ROHM 1st Half 2nd half Device Built and tested (F) (24hrs)sec sec B11/B10b + E field 4.00E−05 1.7.E+05 30 570 B11/B10b (no EField) 4.00E−05 1.8.E+06 2 120

Magnetic Field Used to Orient Molecules

In one or more experiments, it was demonstrated that exposure of acapacitor using pthalocyanine complexes to a strong magnetic field has astrong effect on the internal resistance of the capacitors. A fieldperpendicular to the capacitor electrodes dramatically reduces theinternal resistance of the capacitor from several hundred thousand ohmsto several hundred ohms; conversely, a magnetic field applied parallelto the electrodes dramatically increases the insulation resistance ofthe same, from the original several hundred thousand to many tens ofmegohms.

The application of a magnetic field parallel to the electrodes while thecapacitor is under strong electrical bias has the potential todramatically increase the insulation resistance while keeping the highdielectric constant (as high as 30 million and over) of thepthalocyanine containing complex dielectric material. An insulationresistance (IR) value of 100 mega-ohms/cm² will result in a practicalelectrical storage device for solar cells, and an IR of 10,000 to100,000 megohms will result in the widespread replacement ofconventional batteries in most applications. Experimental results areillustrated in TABLE X. The B field had an impact on resistance.

TABLE X C ROHM Device Built and tested (F) (24hrs) B11/B10b + B field2.50E−06 8.0.E+06 B11/B10b 4.00E−05 1.8.E+06

In one or more embodiments, a silver containing polymer thick film pasteis printed onto a ceramic substrate such as 96% alumina, followed by oneor two prints of the dielectric material, and then a top silverelectrode. The silver electrode paste comprises 80% silver powder withan average diameter of about 3 microns, 15% polymethylmethacrylate, and15% Eastman Texanol™. The dielectric paste comprises 33% copperphthalocyanine pigment, 10% polyalphamethylstyrene, and 57% 1-octanol.

In another example, a silver containing polymer thick film paste isprinted onto a ceramic substrate such as 96% alumina, followed by one ortwo prints of the dielectric material, and then a top silver electrode.The silver electrode paste comprises 80% silver powder with an averagediameter of about 3 microns, 15% polyethyl methacrylate, and 15% EastmanTexanol™. The dielectric paste is composed of 33% copper phthalocyaninepigment, 5% ethyl cellulose, and 57% Texanol.

In terms of applicable substrates, any material may be used that willnot flex to the extent that the dielectric layers will crack or becomeporous. Stiff circuit board and ceramic substrates such as those used inthin and thick film fabrication are examples of suitable substrates.

Polyimide and Mylar films can be used as well. In these cases the filmsare fixed to a rigid substrate or fixture during the application of thepaste. The Polyimide can be removed from the fixture and rolled with theUHCC-dielectric to form cylindrical shapes or cylindrical capacitors.

In regards to organic Ink Binders, the resins suitable for the printingink are used at very low levels such as one (1) to two (2) percent ofsolids volume in one or more embodiments so as not to interfere with thehigh dielectric constant, which may be referred to herein as a purefilm. Typical resins are ethyl cellulose and nitrocellulose. Resins thatvolatilize at or below 200 degrees C. are particularly advantageous. Anespecially attractive binder for these compositions ispoly-alphamethylstyrene, which completely volatilizes at temperaturesbetween about 150 and about 200 degrees, leaving a substantially purecopper phthalocyanine film after sintering, thus maximizing capacitanceof resulting capacitors.

In regards to Ink solvents, the ink solvent may be relatively slowdrying and suitable for screen printing. Examples of suitable solventsare Dowanol® PPH, alpha-terpineol, octanol, decanol, or Texanol®.

In regards to dielectric materials, the dielectric material for the oneor more supercapacitors disclosed herein is chosen from a class ofmaterials that has an extremely high dielectric constant from static (0Hz) to low and to ultralow frequencies such as 10 Hz to 0.0001 Hz. Thematerial used may be copper phthalocyanine. However, the material can beany material in which there is extensive electron delocalization and anability to distort the molecular structure under an electrical field.The low dielectric relaxation time enables the use of these materials assuper-capacitors.

In regards to paste preparation, the resin and solvent are combined andheated to about 100 degrees C., with stirring, until the resin has beendissolved to form the paste vehicle. Then the pigment (copperphthalocyanine) is added to the vehicle to a level of about 30 to 40volume percent. The mixture is mixed in a device such as a countertopmixer and dispersed on a device such as a roll mill. Viscosity isadjusted to a suitable range to facilitate screen printing.

For the capacitor fabrication, a bottom electrode is deposited, and inone or more embodiments, may be deposited by a manner such as screenprinting a polymer silver thick film paste. The print is then cured inan oven at 150 to 200 degrees C. One or two layers of dielectric pasteare then printed over the bottom electrode, after which the dielectricprints are cured at between about 125 degrees C. and about 175 degreesC. A top electrode is applied in the same manner as the bottom electrodeand finally cured, resulting in a finished capacitor.

An illustration of the paste preparation is provided in FIG. 1. Rawingredients are mechanically mixed under thermal energy to assist in themixing operation. The resin and solvent are combined and heated to about100 degrees C., with stirring, until the resin has been dissolved toform the vehicle.

An illustration of the manner provided for pigment mixing is illustratedin FIG. 2. The pigment such as copper phthalocyanine or the soliddielectric material, special organic, special organometallic, mixture oforganic to organometallic and mixtures or mixtures of dielectricadditives with special organic or special organometallic are added tothe vehicle to a level of about 30 to 40 volume percent. The mixture ismixed in a device such as a Kitchenaid® countertop mixer and dispersedon a device such as a Ross three roll mill. Viscosity is adjusted to asuitable range to facilitate screen printing.

FIG. 3 provides an illustration of a paste being roll milled to form adielectric material. This step can be followed by die cutting.

The thermal treatment of the mixed layer is subjected to a thermaltreatment having heating steps and cooling steps that lead to controlledmorphology of the film. As illustrated in FIG. 4, the various thermalplateaus (TPs) are designed to yield a good film given a starting rawmaterial chemistry. Once the film is screen printed or milled on to arigid substrate or a flexible substrate, a TP-1 of solvent removal isapplied typically in the range of 80° C. Vacuum can be used to furtherassist in the removal of volatiles. This lessens the chance ofsubsequent pop-corning or cratering in the film during subsequent steps.A TP-2 in the range of 180° C. can be used to allow the organic ororganometallic semiconductor to settle in with the dielectric powder andenable the removal of any trapped air pockets. Ultrasonication in thepresence or absence of vacuum can be helpful in the removal of voids orpockets. The use of controlled atmospheres can be applicable. Oncesufficient time is allowed at this temperature, a subsequent step ofTP-3 is applied. The better results are observed when the sinteringtakes place in the thermal plateau having a temperature about half themelting point of the organic or organometallic material. Sufficient timeis allowed to allow material flow and the establishment of asubstantially continuous phase. In this thermal plateau an additionalheat source can be used such an IR lamp or other lamps such as thoseused in rapid thermal processing of semiconductors. The continuous phaseis driven to a high enough temperature to form a smooth surface withminimal defects trapped in the film. The cooling phases can be designedin TP-4 to promote nucleation and growth of small crystalline phases.The crystalline phases can be seeded by choosing a dielectric additivematerial having a lattice structure conducive to the formation of smallcrystals. Furthermore the heating apparatus can be equipped with anebulized spray of small particles having a lattice structure conduciveto crystal formation in the now sintered organic or organometallicsemiconductor. The nucleation of small crystals is followed in TP-5which can be designed to grow crystals at a rate that allowmorphological control of the crystalline film. Furthermore, in lieu of,or, in addition to the techniques described supplementing the thermaltreatment, all of TP-2, TP-3, TP-4 and TP-5 can be conducted under theinfluence of a strong electric field to promote preferential alignmentof the special organic, organometallics, or mixtures thereof. Theelectric field magnitude can be in the range of 1 Killo-Volt per meterand greater. A magnetic field can also be used having a strength ofabout 0.1 Tesla and greater to promote alignment of a dielectricmaterial having paramagnetic properties that leads to alignment of thedielectric which in turns aligns the special organic or organometallic.

FIGS. 5A, 5B, and 5C illustrate one or more embodiments of a top view ofthe build-up of a capacitor where two electrodes are of different areaof size. The bottom electrode, 13, the film made of an ultra-high chargecapacity dielectric material according to one or more embodimentsdisclosed herein after sintering, 14, and the bottom electrode, 15 areshown.

FIG. 6 provides a cross-section of one or more embodiments of acapacitor showing a thin electrode, 16, a sintered film of organic,organometallic, or mixture thereof having a continuous phase, 17, andanother electrode of the same or of different thickness, 16′.

FIG. 7 illustrates one or more embodiments of a capacitor cross-sectionshowing a capacitor with an interface material layer 18, consisting of asilver doped copper phthalocyanine layer. In these one or moreembodiments, a thin silver electrodes of 5 micron thickness, 16″, areformed around the material dielectric 17′ of 10 microns thickness havinginterfaces build on the surface. A sintered film of copperphthalocyanine having a continuous phase and having a thickness of 10microns, 17′, is first doped with silver to form the interface layer,18.

FIG. 8 illustrates one or more embodiments of a capacitor materialhaving sintered film of copper phthalocyanine having a continuous phaseand crystallized using nucleation and growth after special thermaltreatment, 19.

FIG. 9 illustrates one or more embodiments of a capacitor materialhaving sintered film of copper phthalocyanine having a continuous phaseand substantial alignment by the application of an electric field duringprocessing, 20

FIG. 10 illustrates one or more embodiments of a capacitor havingsintered film of copper phthalocyanine having a continuous phase withnano size (or larger) dielectric fillers, 21.

FIG. 11 illustrates one or more embodiments of a capacitor having asintered film of copper phthalocyanine, 22, sandwiched between two filmshaving a continuous phase with nano-size (or larger) dielectric fillers,21.

In FIG. 12, an illustration of one or more embodiments of an angleddielectric that is multilayered using items 21 and 22 is provided.

FIG. 12 provides one or more embodiments of an illustration of achemical structure of phthalocyanine.

FIG. 13 provides one or more embodiments of an illustration of achemical structure of copper-phthalocyanine.

FIG. 14 provides one or more embodiments of an illustration of achemical structure of Pyrene.

FIG. 15 provides one or more embodiments of an illustration ofFluorescein.

FIG. 16 provides one or more embodiments of an illustration of Anthrone.

FIG. 17 provides one or more embodiments of an illustration of anOrganometallic compound.

FIG. 18 provides one or more embodiments of a parallel plate capacitorcharged under DC conditions.

FIG. 19 provides one or more embodiments of a parallel plate capacitorcharged under AC conditions. Two opposite field orientations are shown.

FIG. 20 illustrates one or more embodiments of a dielectric materialoccupying a volume and surface area between the electrodes. Theintroduction of a dielectric material between the electrode leads to theformation of dipoles opposing the electric field in the capacitor. Thisleads to the ability to store more charges in the capacitor.

FIG. 21 provides a chart depicting that the dielectric constant (orcharge storage capability) as well as the loss factor are both dependentof frequency. As frequency is increased the loss increases and passes apeak value. The dielectric constant has two different values before andafter the peak of the loss factor. The dielectric constant enters aplateau regime of lower values than before the peak in the loss factor.The low frequency regime prior to reaching a frequency that renders thecopper Phthalocyanine static in oscillating electric field is thepreferred regime of operation.

The remaining figures are directed towards experimental data and one ormore devices and structures disclosed herein.

Examples of High K Dielectric Materials

High K dielectric materials used in electronic applications are commonlyceramic materials such as ferroelectric Barium Titanate, which has a Kof a little over 3000, or a relaxor material such as lead Titanate,which has a dielectric constant of over 10,000, but has a poorer highfrequency performance in the gigahertz frequency range thanferroelectrics. Thus, for high frequency applications, barium titanateBaTiO3 is much more commonly used than lead titanate.

Organic materials with high K are resins such as cyanoacrylates. Theseare commercially available with K of about 10 to as high as 50, andcould be developed to produce filled barium titanate composites withdielectric constant of 100 to 500. Copper phthalocyanine pigments haveextremely high dielectric constants up into the million range, but verypoor usable frequency range at high K. This disclosure concernsprincipally copper phthalocyanine based devices for battery replacementapplications but in principle is not limited to these materials. Sincethe frequency of charge and discharge of a supercapacitor used for powerstorage is on the order of tens to many thousands of seconds, frequencyresponse is not an issue in power storage applications.

Materials for Filled Capacitors

A number of materials for fabricating filled capacitors are commerciallyavailable. These materials are in the form of finely ground (usually)ferroelectric powders commonly ranging from about 0.3 micron to about 3to 5 microns average particle size. These materials place a high Kdielectric material finely divided into an organic matrix, which usuallyis coated as a ceramic slip and dried to make a “tape” which is combinedwith electrode layers and fired usually above 1100 degrees C. Theorganic fraction of the composite is burned out, and the ceramic powdersare sintered to form a ceramic grain structure with close to 100 percenthigh K dielectric material. The typical MLC capacitor consists of manylayers of these dielectric/electrode materials, up to about 500 layers.These materials have a K of about 3000. Filled non-fired systems containhigh K dielectric powder dispersed in an organic matrix and are screenprinted or stenciled onto a substrate without the need for hightemperature firing, as is necessary with dielectrics made of 100 percentferroelectric or relaxor materials. These ceramic/organic non-firedcomposites commonly have a K of 30 to 60.

Multiple particle size mixtures can be used to fill void spaces betweenparticles more completely than by using a single average particle sizefiller. Empirically determined size ratios and volume fraction ratiosare 3 to 4 to 1 size ratio and about a 5 to 1 size ratio. Three discreteparticle size fractions are even more effective than a bimodal mixture.

Ferroelectric Vs. Relaxor Ceramic Dielectrics

Ferroelectrics and relaxors are two types of ceramic dielectric.Ferroelectric dielectric materials, for example, barium titanate, have ahigh dielectric constant of 3000 to 3300, a very fast response time, andtan delta and K are relatively constant with increasing frequency.Relaxors, for example, niobium lead titanate, typically have a higherdielectric constant, which may be as high as 18,000, but dielectricfalls off more rapidly with frequency, and tan delta increases withincreasing frequency. Thus, for multi-gigahertz electronic applications,ferroelectrics are more useful.

Building a Filled Dielectric Device

To build a filled system, one would, for example, use barium titanate orniobium lead titanate powder in a mixture with copper phthalocyanine.Since the copper phthalocyanine melts at about 240 degrees C., it can besintered in an oven to form a matrix around the filler material. Thedielectric constant of the filled system can be approximated using theequation:log K(comp)=log K(matrix)*vol.fr.(matrix)+log K(filler)*vol.fr(filler)

where K=dielectric constant and vol.fr. is the volume fraction of therespective component. To start, a bottom electrode is screen printedonto a substrate. The dielectric components are dispersed into anorganic vehicle that burns out relatively easily below 200 degrees C.,leaving very low residue. The mixture is then stenciled or screenprinted onto the substrate over the electrode, dried, and then thecopper phthalocyanine powder is sintered to form a continuous matrixsurrounding the ceramic dielectric powder. A top electrode is thenprinted over the dielectric composite forming a capacitor, which canthen be electrically tested.

Thick Films

Thick film materials are commonly prepared from powders in the range of0.3 to 5.0 micron average particle size, depending on the application.These powders are dispersed into an organic vehicle to form a printingink, are printed onto a suitable substrate, and can then be sintered toform a continuous film at temperatures well below the melting point ofthe powders. Thus they are more easily processed at lower temperaturesthan larger particles or discrete structures.

Sintered thick film materials such as dielectrics do not usually form acontinuous film; rather, they sinter into a structure with grainboundaries, and usually there is residual porosity due to the presenceof printing defects and large particles in the powders used, that causevoids in the film. To counter this phenomenon, multiple prints ofdielectric are used. Since the probability of two tiny defects occurringin exactly the same position in two successive layers is vanishinglysmall, the problem is essentially solved. A very small amount ofporosity is often tolerable, the resulting electrical degradation beingreferred to as leakage current, and the lower it is, the better thedielectric. Other performance parameters measured on thick filmdielectrics are K, tan delta (<0.003 is acceptable), and breakdownvoltage (typically 1000 to 4000 volts). The K of fired dielectrics istypically 1,000 to 3,000 for barium titanate based dielectrics.

Cylindrical Form Factor

To produce a cylindrical form factor, the dielectric can be printed on athin polymeric film such as polyimide that will tolerate high curingtemperatures easily, as a sort of scroll. The dielectric can be printedon both sides of the polymeric substrate, then rolled up to produce acylindrical form factor compatible with electrolytic capacitors.

Applications:

The following applications are non-limiting and a non-exhaustive list ofmanners and products in which the one or more capacitors and dielectricmaterials disclosed herein may be employed:

Electric Car

A vehicle having a motor for propulsion powered by electrical energythat is used as the primary or exclusive mean of moving the vehicle orthat is used in conjunction with a motor powered by a combustible fuel.

The battery electric vehicle has many advantages including reducedpollution and green house gases by departing from a fossil fuel andpossibly leading to a 30% reduction in carbon dioxide emissions.

An on board battery pack can be replaced with one or more capacitorsdisclosed herein. The battery pack may include a series of tiles likesuper-capacitors connected together to provide sufficient energy for thevehicle and small enough that no one tiled super-capacitor havingexcessive energy.

Furthermore, the one or more capacitors disclosed herein enables a rapidcharging of the tiled super-capacitors when compared to standardbatteries used in battery electric vehicles.

Solar Panel

A photovoltaic based solar panel can convert the photonic energy fromthe radiation of the sun into electric energy. These solar panels can beused in solar plants and in residential buildings. The PV cells arearrayed in various configurations and linked together to form a panel.In turn panels can be arrayed and electrically connected together toyield more electrical energy. The photovoltaic installations includeinverters and batteries. These photovoltaic systems can be used for offgrid applications or in solar panels in vehicles and spacecrafts.

The one or more devices disclosed herein lead to efficient energystorage and enables one or more effective methods for transporting suchenergy from one geographical location to another. The one or moremethods are more effective and efficient compared to transmitting theenergy through copper wires and the like.

Appliances

Small appliances that are portable and semi portable that are poweredusing electrical energy can be powered using electrical energy stored bya capacitor according to one or more embodiments disclosed herein. Theelectrical appliance powered by the capacitors according to one or moreembodiments disclosed herein may enable full portability of theseappliances without being plugged into a residential electrical plug.

Personal Digital Assistant and Portable Computers

Most batteries used in computers and PDA are based on lithium-ionbatteries in which an ion moves across two oppositely chargedelectrodes. The present invention leads to small tiled super-capacitorscapable of storing energy and powering consumer electronics, PDAs, andportable computers.

Transportation

In applications related to energy storage for providing electricity toutilities, businesses and private customers, storage systems are neededfor covering peak demand, for balancing the grid, and for handlingintermittencies.

Supercapacitors have the potential to support the stated needs for aconventional grid, and can also be used to support solar and wind energysources which suffer from weather-related intermittencies. Clearly therole of supercapacitors in handling weather-related intermittencies inwind and solar energy generation will depend on the energy storagecapacity. For the latter, the utilities use natural gas turbines toovercome the drop in power from weather-related intermittencies.However, gas turbines have a spin-on time of 10 minutes before producinga steady supply of electricity. Consequently a critical application ofsupercapacitors would be to provide electricity to cover that 10-minuteramp-up time.

PV generation of electricity is highly weather dependent andunpredictably intermittent on very fast scales (sub-seconds) and overshort (minutes) or long (hours) time periods.

One or more capacitors described herein could be stacked on the backs ofeach solar module to provide electricity for a 10 minute dead-time, orany other desired time period. Typical solar modules produce between 100and 300 watts of power. A 10 minute full power interval would require20-50 Watt-hours of delivered energy. For one or more capacitors whosevoltage decreases with charge, the required range of energy capacitywould be 40-100 Watt-hours. Another application would be to designseparate banks of supercapacitors to provide the power smoothingrequired for the turbine spin-on periods to cover the weather-relatedintermittencies.

Due to the ease of fabrication of the solid electrolyte materialsdisclosed herein, it is also possible to integrate the supercapacitorinto the cell fabrication at little added cost and build PV modules thatprovide the 10 minute energy back-up function in the same package.

For an integrated PV-supercapacitor device, a typical design wouldrequire the PV solar cell to be in parallel with the supercapacitor witha safety diode placed to prevent back current through the solar cell.The supercapacitor can be mounted or built on the backside electrode.

The diagram shows the backside electrode serving as one of the directsupports for one of the supercapacitor electrodes. The other is mountedon the other side of a perimeter spacer that permits addition of theelectrolyte. Low cost requires that the supercapacitor electrodes befabricated by a process that is fully compatible with the manufacturingprocess for the PV film stack. Metal contacts and electrodes can bedeposited using the same processes as in PV manufacturing.

Elements

The following elements are represented by corresponding element numbersthroughout this disclosure: Solvent, 1; Solid resin, 2; Vehicle duringmixing, 3; Thermal Energy, 4; Mixer, 5; Pigment, special organic,special organometallic, mixture of organic organometallic, 6; Vehicleafter mixing, 7; Paste during mixing, 8; Paste after screen printing orroller milling, 9; Roller milling, 10; Green film (film beforesintering), 11; Thermal Profile, 12; Bottom Electrode, 13; Film aftersintering, 14; Bottom Electrode, 15; Thin Electrode, 16; Sintered FilmOf organic or organometallic or mixture thereof Having a ContinuousPhase, 17; an electrode of the same or of different thickness, 16′;Silver Electrode with 5 micron thickness, 16″; Sintered Film Of CopperPhthalocyanine Having a Continuous Phase (10 microns), 17′; InterfaceLayer Having Doped Silver Layer interface, 18; Sintered Film Of CopperPhthalocyanine Having a Continuous Phase and crystallized usingnucleation and growth after special thermal treatment, 19; Sintered FilmOf Copper Phthalocyanine Having a Continuous Phase and substantialalignment by the application of an electric field during processing, 20;Sintered Film Of Copper Phthalocyanine Having a Continuous Phase withnano size dielectric fillers, 21; Sintered Film Of CopperPhthalocyanine, 22; Layered dielectric at an angle, 23; an electrodehaving a recess around its perimeter, 16-1; Large bottom electrode,16-2; Perforated electrode, 16-3; Aluminum electrode, 16-4; Noveldielectric, 21; Copper Phthalocyanine, 21-1; Zinc Phthalocyanine, 21-2;Copper Phthalocyanine with added BaTiO3, 21-5; Inner Layer, 22; resinwith high polarity, 22-1; resin with high polarity doped with carbon,22-2; Passive metal inner layer (with no bias applied), 22-3; Activemetal inner layer (with bias applied), 22-4; Rubber Gasket, 23;conductive Ink containing carbon black pigments, grahene, or activatedcarbon, 24-1; thin film of copper phthalocyanine deposited on theelectrode using sputtering or evaporation techniques, 24-2; C-Clamp, 25;Electrical probes, 26; Perimeter spacer that permits addition of theelectrolyte, 27; backside electrode of PV panel, 28; p-type or n-typesemiconductor substrate, 29; and semiconductor junction material, 30.

Material Preparation:

In order to prepare a dielectric material according to the one or moreembodiments disclosed herein, several methods for material preparationcan be employed and are described herein.

In a method according to one or more embodiments disclosed herein, twograms of Copper Phthalocyanine dielectric powder were weighed in amixing cup using a five (5) digit balance. A solvent, such as Texanol,was added to the organometallic powder using about a 3:1 ratio andthoroughly mixed by hand. As used herein, organo-metallic may refer to acomplex of a phthalocyanine and a metal. The mixture was thentransferred to between glass plates for shearing dispersion. The gapbetween the glass plates was about two (2) mills thickness. High shearwas successful using two (2) glass plates. A roller mill may also beemployed for imparting shearing forces.

An organic vehicle, such as a mixture of Ethyl Cellulose and Texanol,was added to the mixture of Texanol and Copper Phthalocyanine. Theweight ratio of the Ethyl Cellulose to copper Phthalocyanine was variedfrom 0% (no organic vehicle) to about 12%. Additionally, a silver pastemade from silver powder and Texanol was prepared.

Methods for Applying the Dielectric Material

In order to apply the dielectric material according to the one or moreembodiments disclosed herein, several methods for material applicationcan be employed and are described herein.

In a method according to one or more embodiments disclosed herein, anMPM screen printer may be used to apply the silver paste into a patternto a substrate, such as one commercially available from CoorsTek® ofGolden Colo., to form electrode patterns. After the conductive paste isapplied to the substrates, a thermal treatment may be carried out inorder to drive solvent removal, drying, and curing of the substrate.This process may be utilized to form both the top and bottom electrodes.In a method according to one or more embodiments disclosed herein, thedielectric mixture may be printed on top of the bottom electrodefollowed by drying and curing. Then the bottom electrode having thedielectric on one of its surfaces may be mated with the top electrode.The capacitor hence formed was tested for electrical properties in termsof resistance, capacitance, and its ability to hold charge.

Screen Printing

One or more methods of applying the dielectric material may includescreen printing as disclosed herein. In one or more embodiments, thebottom electrode is formed by screen printing a conductive epoxy on aceramic substrate. The substrate and the bottom electrode may then beheated to cure the conductive epoxy, which in one or more embodimentsmay be heated at or below 80° C. The dielectric may then be printedusing a stencil of appropriately configured dimensions. In one or moreembodiments, the Copper Phthalocyanince mixed with a Texanol solvent andethyl cellulose as the organic vehicle may be printed in consecutivelayers. More than one layer may be printed. For example, in one or moreexperiments, one, two, and three layers of dielectric were printed andthe capacitance and other desired parameters were then tested. Thequality of the film may be inspected using an optical inspectioncapability. Following every print, a partial solvent removal may beused. The removal of solvent(s) may be performed under heat below 80° C.and inert atmosphere. In one or more embodiments, the substrates withthe dielectric were heated to above about 150° C. and below about 310°C. in order to sinter the particles in the material, though in one ormore embodiments, sintering may not be required. In one or moreembodiments, the bottom electrode may be formed by screen printingconductive epoxy on a ceramic substrate. The substrate and the bottomelectrode may then be heated to cure the conductive epoxy. The capacitormay then be formed by assembling the top and bottom electrode with oneor more dielectric layers in between. In one or more embodiments, afterassembly, pressure may be applied to the capacitor in combination withheat and further testing may be carried out to determine desiredelectrical properties. The heat may be applied using a thermode embeddedin a press such is commonly used in thermal compression bonding.

Draw Down the Material

In a method according to one or more embodiments, a Kovar electrode,such as that which is available from the Carpenter TechnologyCorporation of Reading, Pa., may be placed on a glass substrate and aspacer tape having a thickness of about 60 microns may be applied to two(2) out of four (4) sides of the glass substrate. A portion of thedielectric may be deposited on one end of the metal electrode. Thedielectric material may be applied by drawing down the material using aknife, a razor blade, or glass from one side of the electrode to theopposite side of the electrode. The travel direction of the knife orblade may be parallel to the direction of the spacer tape. The materialsmay then be dried and the tape may then be removed to form a straightedge on the electrodes.

In one or more embodiments, the top electrode may be coated with aninterface layer and then mated with the bottom electrode having adielectric deposited thereon to form a capacitor. The two electrodes maybe held together using a clamping device, such as a C-Clamp. The amountof pressure from a clamp may be varied. A representative illustration ofa capacitor formed by one or more embodiments described herein isillustrated in FIG. 22.

In one or more embodiments, two (2) electrodes each of which may have adielectric coating may be dried partially or fully. The two (2)electrodes having a dielectric may be mated together to form acapacitor. The two (2) electrodes may be clamped together using a clampsuch as a C-clamp. In one or more embodiments, an inner layer or abridging layer may be used to matingly engage the two (2) electrodeshaving dielectric coatings applied to them. The inner layer preparationand chemistry were found to be important to the overall operation of thecapacitor and many chemistries were attempted in one or more experimentsdescribed herein.

Metal Foil/Flexible Electrode

According to one or more embodiments, the dielectric material may bedrawn down onto a metallic foil, or metallic sheet. A spacer tape havinga thickness of 60 microns may be used to draw a portion of dielectricand to form a uniform thickness film disposed on the surface of themetallic foil or the metallic sheet. A thermal treatment may then beapplied to controllably heat and controllably cool the dielectric filmformed thereby.

Dispensing

According to one or more embodiments, a dielectric may be applied usingan automated dispenser to one of the electrodes using a controlledweight in a controlled pattern. The electrodes may then be collapsed ontop of one another using a pick and place to obtain a uniform thickness.A spacer material may be placed to prevent shorting of the electrode andto promote the formation of a uniform film thickness. The assembly henceformed may be dried inside the oven.

Organic Vehicle

In one or more embodiments, the amount of organic vehicle used mayincrease the green strength of the dielectric. The higher the content ofthe organic vehicle results in more green strength of the dielectric,whereas the presence of increased organic vehicle results in lessmeasured capacitance. An optimal range of organic vehicle that balancescracks after drying and capacitance build up may depend on thedielectric powder size and powder size distribution, the solvent systemor combination of solvent systems used, and the difference of thecoefficient of thermal expansion between the electrode and thedielectric film.

Thermal Treatment

According to one or more embodiments, thermal treatment may be conductedon the dielectric material using a heated chuck. In one or moreembodiments, the heated chuck may be used with or without vacuum. Argonor Nitrogen may be used to apply a low pressure flow of inert gastowards the dielectric while inside the heated chuck. This method ofdirected gas flow in combination with vacuum may be used to control theenvironment around the dielectric during drying. The heat from the chuckmay be provided to enable ramping up and cooling down the samples in acontrolled fashion. In one or more embodiments, a vacuum oven may not beused. The addition of vacuum to the thermal treatment may be providedfor removing solvents from the dielectric. The drying temperature mayrange from about 40° C. to about 175° C. Depending on the solvent systemused or the combination of solvent(s) used, the drying temperature thatled to the best results varied in one or more experiments disclosedherein. Drying at about 80° C. may be employed in order to avoidcreating cracks in the film. In one or more embodiments, dryingtemperatures as low as about 40° C. may be employed while vacuum isbeing applied and as high as about 100° C. when an inert gas flow isbeing applied. Higher drying temperatures may higher temperatures mayresult in cracks in the dielectric.

Partial Vs. Full Drying

In most cases where the dielectric material was applied to one or bothelectrodes, a full drying, a partial drying or no drying at all wereinvestigated in one or more experiments in terms of impact of thecapacitance build up.

The surface roughness of the dielectric may have an impact on thecapacitance values of a capacitor. For example, when two (2) electrodeshave been coated with the dielectric material and then dried fully underheat and vacuum, an air pocket may be formed at the interface when thetwo (2) electrodes are engaged together. This air pocket may havenegative effects on the capacitance values of the capacitor.Accordingly, various methods and steps may be taken in order to minimizethe air pocket. For example, in one or more embodiments, the top andbottom electrodes may be mated and held together using a clamp such as aC-clamp. In one or more experiments, the air gap may be minimized byhaving the materials partially dried rather than fully or not dried atall before clamping. A small amount of residual solvents may be used tohelp bridge the dielectric materials when they are mated and heldtogether.

Applying Compression C-Clamp

In one or more experiments, it was determined that applying compressiveforces to the electrodes may help during the drying process. Thecompressive forces may be derived using weights on top of the capacitorsor by using a clamp such as C-clamp to maintain compression. The amountof pressure from the C-Clamp may be varied and in some experiments maymake a difference and in other experiments it may not make a difference.

In one or more experiments, a combination of solvents that lead to theformation of a good film having a good packing factor between theorganic and organo-metallic particulates may be employed. It wasdetermined that the compression induced by the sequential removal ofmultiple solvents exceeded the compression achieved by pressure from aC-clamp.

Particle Size:

The bi-model or a tri-model distribution of particle sizes may lead toan increase in density or the packing factor. According to one or moreembodiments disclosed herein, a mixed particle size system suitable tomaximize the packing factor that may facilitate particle to particlecontact may be employed. The dispersion and shearing may also beimportant in the final properties.

An example is cited that contrasts two (2) copper phthalocyanines withdifferent particle size distributions that were obtained from two (2)different vendors. The results from the copper phthalocyanine obtainedfrom AESARs was in the range of 200 nm while the copper phthalocyaninewas in the range of 500 nm and yielded a better film. The compaction ofa powder depends on the particle size distribution. The currentdielectric paste preparation includes a mixture of inorganic dielectric,organic polymers, and organometallic particulates. The packing factor isno different than mixed particle systems in that higher densificationmay be obtained using a suitable tri-modal distribution.

Thermal Treatment

In one or more experiments, it was discovered that upon heating thematerial, the particles forming the dielectric material start sintering,meaning that the materials begin “necking” which may be the first stepof densification. This densification was observed at about 150° C. andabove. It was also determined that in one or more experiments, thepercentage of vehicle contained in the mix may have an effect oncapacitance. In one or more experiments, it was determined that thehigher the temperature and the faster the heat rate, the more crackswill be observed after drying. The particles are prone to oxidationwhich leads to an increase in resistance and a reduction of capacitance.Therefore, an oxygen free atmosphere is most desirable because even asmall amount of oxygen may lead to oxidation. However, in one or moreexperiments, good results were obtained even when the materials wereprocessed in air.

Film Crack Healing

A mix of copper phthalocyanine or other organometallic particles with ahigh solvent content may be used to fill and heal cracks since the lowviscosity mixture may carry particles inside to impregnate the pores andlead to higher densification. Multiple impregnation steps may beperformed on the dielectric material to reduce porosity and increasedensity. Each of the multiple impregnation steps may be followed by asolvent removal step. These one or more steps may be provided to densifythe porous material and increase the dielectric particulates content toreach a final form, with the desired results being a defect freedielectric film deposited on an electrode.

According to one or more embodiments, a low viscosity solvent such asTexanol, Ethanol, or Acetone may be used and encapsulated using a rubbergasket such as that which is illustrated in FIG. 23. This may lead to anincrease in capacitance without a decrease in resistance. A pure solventmay increase the potential of being flammable and may have otherdrawbacks. According to one or more embodiments, porous electrodes maybe employed to allow for a volatile removal path for the varioussolvents.

Electrical Measurements

In one or more experiments, an HP meter 34401A available from HewlettPackard, a DC power supply HP6634B (0-100V & 0-IA), a triple output DCpower supply HP E3630A 0-6V, 2.5 A/0-+/−2.0V, 0.5 A, and a Radio Shack(catalogue #22-811) digital multimeter for capacitance measurementshaving a maximum capacitance measurement of this instrument was 40micro-Farads were used. Any values greater than 40 micro-Farads resultedin an Over Flow signal in the meter. The capacitors built using 12 mm×12mm kovar electrodes in the one or more embodiments disclosed hereinshowed an over flow response.

In one example, on an electrode measuring 8.0 cm by 2.0 cm, thedielectric material was drawn down and dried. The top electrode was 1.2cm by 1.2 cm. The measured resistance was 158.2 kilo-ohms and thecapacitance was over 40 micro-farads. In one or more embodiments, morethan one top electrode may be coupled with the large bottom electrodesuch as that which is illustrated in FIG. 24 in which the bottomelectrode 16-2 may have three smaller top electrodes 16 and the noveldielectric 21.

In one or more experiments and/or embodiments in which a metal foil wasused, after the dielectric material was drawn down and dried, the metalfoil was wrapped around a ceramic substrate and adhesively bonded to it,a top electrode was then mated with the outer most surface of thedielectric layer and held in place using a C-clamp to form a capacitor.

In one or more experiments in which copper phthalocyanine having a 3% byweight ethyl cellulose was used as the organic vehicle, a capacitance ofover 40 micro-farads was measured. In these one or more experiments, thearea of the electrodes was 0.00027225 square meters and the distancebetween the electrodes was 20 microns, a dielectric constant of 3.34×10⁵was measured.

In one or more experiments in which copper phthalocyanine in one layermixed with Glycerol and copper phthalocyanine mixed with zincphthalocyanine in the other layer bridged with a dried carbon inkcontaining carbon black, the dielectric constant was calculatedaccording to the table below. Hence we have a dielectric constant around50 millions in this example. Other examples were shown to lead to highervalues. Experimental results for dielectric constant k are illustratedin TABLE XI.

TABLE XI C 0.000833333 Farads Co 1.6896E−11 Farads ko    8.8E−12 — L10.012 L2 0.012 m2 D 0.000075 m2 k 49,321,338

Non-Linear Behavior

In one or more experiments, it was determined that by changing thematerial composition of the dielectric material, the resistancedecreases with applied bias.

Super-capacitors have the ability to produce large power density (perunit weight or unit volume) by releasing stored charge quickly. Existingdevices are not too far from batteries in this respect. However, energydensity has always been a disadvantage. In order to achieve high energydensity, large amounts of charge must be stored in the device. In makingsuper-capacitors that hold large amounts of charge, either of threemethods are used including increasing the surface area of theelectrodes, increasing the dielectric constant of the electrolyte or thematerial between the electrodes to store more charge or polarization,and/or designing a hybrid super-capacitor/battery system in which theelectrodes react with the electrolyte.

All three approaches have been used in the past without success forincreasing energy density. The last option suffers from the same lifecycle limitations as do batteries.

The one or more capacitors and other devices disclosed herein increasethe stored charge or polarization in the electrolyte in order to producea net higher energy density. This is accomplished through the use ofmetal phthlocyanines as described in the one or more embodiments of thisinvention.

As the material between the electrodes stores charge, this forces theelectrodes to hold enough charge to produce a net-zero electric field inthe entire device. Increasing the charge or polarization in the materialbetween the electrodes increases the internal electric field and causesthe electrodes to hold more charge. The total amount of stored charge inthe super-capacitor and its consequent energy density is thereforedependent on the total charge and polarization stored in the materialbetween the electrodes. Breakdown voltage limits the total stored chargeand leakage current decreases it with time.

Conventional copper phthalocyanine and mixtures of other phthalocyaninessuch as zinc phthalocyanine have relatively high leakage current at onemil thickness in devices. Also, the relationship between charge storedand applied voltage which is commonly linear in dielectric materialsdecreases with increasing voltage applied to devices. Voltage breakdownis not a problem; the devices withstand 100 volts per mil easily, andleakage only increases linearly with increasing voltage.

The nonlinearity of these metal phthalocyanine mixtures is enormous;when charge storage is estimated by comparing the half life of thesematerials with decreasing voltage during discharge of these metalphthalocyanine containing devices.

the discharge behavior of a typical device. Half life increasesenormously as the capacitor discharges, from seconds at 12 volts to daysat under 0.5 volts. And at 0.2 volts, based on time to recharge, weestimate that about 30% of the charge still remains in the device aftermany days Comparing this behavior to that of a linear capacitor (chargeand voltage vary inversely and linearly), this is extremely different,and this behavior can be used to the device maker's advantage. Forexample, by increasing dielectric thickness two orders of magnitude, ina linear capacitor the capacitance is reduced by 99%, whereas it is onlyreduced by about two thirds in devices using our metal phthalocyaninemixtures. Since the effective dielectric constant of our MPC (metalphthalocyanine) devices is in the hundreds of billions, a two thirdreduction in charge storage with its concomitant increase in half lifeand other properties is a very worthwhile tradeoff.

Increasing the voltage by two orders of magnitude increases energystorage density by a factor of 10,000, disregarding the loss due toincreased thickness. By making the capacitor two orders of magnitudethicker, the net energy storage increases substantially aftersubtracting charge loss due to increased thickness. The increase may beover three thousand fold, and the other device characteristics such asinsulation resistance, Q, and breakdown voltage are also greatlyimproved. Continuing the two orders of magnitude comparison, the energydensity per unit weight of the thicker device is 33× that of the thinnerdevice. Calculated energy density per pound of such a device is about100× that of a lithium ion battery. Thus, a 6 pound MPC device maytheoretically replace the 600 pound lithium battery found in electricvehicles.

Impact of Dielectric Thickness

A capacitor was build using one layer thickness of the novel dielectric.The same novel dielectric was used to build a five layers for the novelcapacitor. Surprisingly, the charge storage was very good and decay timewas excellent. The novel dielectric allows increased spacing between theelectrodes of a capacitor without detrimental penalty to the chargecapacitance or decay time. This is atypical behavior. As can be seen,the five layer thickness capacitor worked.

As illustrated in TABLE XII the half life was over 2 hours even for adielectric material having five times the thickness (150 microns)compared to the typical 30 microns used in single layers. This result isremarkable and the novel dielectric has a solid electrolyte likebehavior and charge storage is maintained with thickness.

TABLE XII Time voltage 0.1 1.63 0.5 1.5 1 1.44 2 1.38 4 1.34 5 1.33 101.29 15 1.27 20 1.24 32 1.2 60 1.12 75 1.07 90 1.04 141 1.03 106 1.01129 0.996 135 0.956

Increasing Resistance & Capacitance

In one or more experiments, zinc phthalocyanine was added to copperphtahlocyanine in order to increase resistance of the dielectricmaterial. In one or more experiments, a formulation having a 9:1 ratioof copper phthalocyanine to zinc phtahlocyanine was prepared, disposedonto a capacitor, and tested for resistance. The material mixture wasdrawn down on electrodes. The top electrode was coated with a purecopper phthalocyanine and the bottom electrode was coated with theformulation having a 9:1 ratio. The electrodes were mated and held usinga C-clamp and measured. Similarly other compositions having variousratios of Zinc Phthalocyanine to Copper Phthalocyanine were prepared andthese included ratios of 1%, 3%, 10%, and 100%. The 100% compositionmeans no Copper Phthalocyanine was present and the composition was pureZinc Phthalocyanine. The resistance of the compositions is illustratedin TABLE XIII:

TABLE XIII Zinc Copper Resistance Phthalocyanine Phthalocyanine (k-OHM) 1% 99% 1,000  3% 97% over 1,000,000  10% 90% over 1,000,000 100%  0%over 1,000,000

In one or more experiments, it was determined that the addition of ZincPhthalocyanine was effective for increasing the resistance of theoverall dielectric which is favorable provided that the mixturemaintains high capacitance. In one or more experiments, the addition ofMagnesium Phthalocyanine and Nickel Phthalocyanine were also tested andyielded similar results in that the resistance is increased by virtue ofmismatch in the electronic orbital or a mismatch in conductive pathwaysbetween the various materials while the capacitance was maintained byvirtue of the compositional selection.

In one or more experiments, a capacitor was developed using two (2)layers including a first dielectric layer of suitable composition, suchas pure Copper Phthalocyanine, that was applied to the top electrode anda second dielectric layer of suitable composition, such as CopperPhthalocyanine doped with Zinc Phthalocyanine, that was applied to thebottom electrode. It was determined that the properties of the capacitorperformed best when the first dielectric layer and the second dielectriclayers have different compositions rather than the same composition. Inone or more experiments, it was determined that the film quality impactsresults as more cracks led to high leakage currents.

In one or more experiments, a capacitor having improved characteristicswas found when the dielectric layers to be mated were bridged using aninner layer 22 of suitable compositions as illustrated in FIG. 29. Thecopper Phthalocyanine 21-1 was applied to electrodes 16 and the suitableinner layer. In FIG. 30 for example the novel dielectric CopperPhthalocyanine with added BaTiO3 (21-5) has an inner layer made of aresin with high polarity doped with carbon (22-2).

The subject of which is addressed herein in one or more experiments toincrease both the resistance and the capacitance.

Different Dielectric Layers

In one or more experiments, a device having two (2) dielectric layersand an interface by the electrode was built as illustrated in FIG. 25A.As illustrated, a copper phthalocyanine layer (21-1) was placed on topof electrode (16), another dielectric layer of zinc phthalocyanine(21-2). The capacitor hence formed having two different dielectriclayers have better decay time. FIG. 25B shows the two halves of thecapacitor mated together. The capacitors were electrically tested usingelectric probes (26) while held together using a compression device (25)as is illustrated in FIG. 26.

Diode-Like Behavior:

In one or more experiments, it was determined that when only oneelectrode is coated the capacitor may exhibit diode-like behavior. Theresistance as measured in one direction is different than the resistancemeasured in the opposite direction. This diode-like behavior may beengineered to yield desirable devices having charge flow dominated inone direction. An illustrative example of a capacitor exhibitingdiode-like behavior is illustrated in FIG. 27.

In one or more experiments, the biasing under voltage was done in suchmanner to have the electrode coated with an interface being the negativepole of the capacitor. In one or more experiments, the biasing undervoltage was done in such manner to have the electrode coated with aninterface being the positive pole of the capacitor. Each of thecapacitor device in the one or more experiments exhibited a diode likebehavior since both charge storage and resistance became orientationdependent.

In some cases as illustrated in FIG. 27A illustrates a capacitorexhibiting diode-like behavior, according to at least one embodiment ofthe invention where the bottom Aluminum electrode (16-4) was coated withan aqueous ink filled with carbon black (24). The biasing of theelectrodes is case-1 was such that the A1 electrode was negativelycharged and kovar was positively charged. In case-2 the biasing of theelectrodes was such that the A1 electrode was positively charged andkovar was negatively charged. In case 1 the resistance was 700 k-Ohm andthe capacitance was 1.6 nano-Farads. In case 2 the resistance was 115k-Ohm and the capacitance was over 40 micro-Farads. Hence the diode likebehavior was demonstrated.

FIG. 27B illustrates a capacitor exhibiting high capacitance having twoKovar electrodes (16) coated with an aqueous ink containing carbon black(24), according to at least one embodiment of the invention where thetwo layered dielectric are different and sufficiently mismatched as isthe case of Copper Phthalocyanine with added Glycerol (21-3) and ZincPhthalocyanine and Copper Phthalocyanine mixture (21-4).

In other cases as illustrated in FIG. 27C a capacitor exhibiting highcapacitance having two Kovar electrodes (16) coated with an aqueous inkcontaining carbon black (24) and an inner layer of a dried aqueous inkcontaining carbon black (24), according to at least one embodiment ofthe invention. The conductive ink containing carbon (24) used forcoating the electrodes (16) were formulated using various carbonsincluding carbon black, activated carbon, graphene that showed goodresults either on top of a electrode or as an inner layer (22).

In one or more experiments, the texanol solvent is removed at a dryingtemperature of about 80° C.; however, glycerol remains in the dielectricsince it has a boiling point much higher than the drying temperature.This step may be used to keep the dielectric particulates in dispersionin the media.

Multiple Solvents and Pressure Application

In one or more embodiments, a double or triple solvent system may beused to achieve enhanced compaction of the organic and organo-metallicparticulates at an increasingly elevated temperature as one solvent isremoved at a time which leads to increasingly higher compaction of theparticulates due to the different boiling points from each solvent. Inone or more experiments, a triple solvent system was used and consistedof a mixture of texanol, tripropylene glycol, and glycerol. This step ofusing multiple solvents was conducted in one or more experiments withpure Copper Phthalocyanine and with a combination of Zinc Phthalocyanineand Copper Phtalocyanine.

A manner of applying pressure to the particles within the dielectricfilm leads to the predisposition of said particles to enter into contactfollowed by necking at elevated temperature and finally densificationand mass transport from one particle into another. One manner ofapplying pressure may be to use a triple solvent system. Each of thesolvents has a distinct evaporation temperature or boiling point. As anexample according to one or more embodiments, a four solvent system maycontain water, Texanol, Tri Propylene Glycol, and Glycerol. As waterevaporates at 100° C., the particles remain under the Texanol and TriPropylene Glycol. When Texanol evaporates, the particles push againstone another to remain under the Tri Propylene Glycol. When the lastsolvent is removed, then the particles go under considerable pressure toavoid air since the surface energy of particles is lower when they arein contact with a solvent as opposed to being in air.

In one or more experiments, it has been determined that the quality ofthe film and the intimate contact between adjacent particles control theelectrical properties of the film and specifically the leakage currentthat happens within the film. It has also been determined that thecharge storage capability of the film is compromised if the filmcontains defects such as crack or holes.

In one or more experiments, the dielectric layers were heated to a lowtemperature to remove solvents with heat recipes that minimize filmcracking. In one or more embodiments, the layers were heated to about60° C. under vacuum, and a film made according to these one or moreexperiments exhibited improved characteristics. In one or moreexperiments, the layers were heated to 80° C. in a convection oven. Attemperatures above 80° C., the film cracks that are observable after thedrying phase are accentuated and the addition of stabilizing agents isnoticeable. In one or more experiments, it was determined that CopperPhthalocyanine films having added Glycerol and dried at temperatures of60° C. exhibited much less drying defects than those at elevatedtemperatures and without Glycerol.

In one or more experiments, the dielectric layers of various mixturesand chemical compositions that were heated to 150° C. and above began todensify. The particles entered into a necking process and theCapacitance was developed to a greater extent. The films that were driedat 60° C. and then heated to at least 150° C. under pressure in a viceunderwent limited to no-cracking followed by more densification. Thisled to the formation of a densified film made of Copper Phthalocyanine.This passage from a film to a densified film resulted in increasedcapacitance. The films using Glycol in the mixtures exhibited much lessdefects. In one or more experiments, the pressure was applied using avice and then placed in an oven and sometimes applied using a hotiso-static press such as thermal compression bonding.

Perforated Electrodes:

In one or more embodiments, an electrode may be perforated (16-3) toenable the evaporation of solvents through the perforations. Thedielectric (21) is applied to another electrode (16) and mated with thecoated perforated electrode (16-3). This method may be used to collapsetwo (2) halves of a capacitor and then dry the solvent post assembly ofthe capacitor. An example according to one or more embodiments isillustrated in FIG. 28

Biasing:

In one or more experiments, an electric field of up to about 3000 Voltswith low current was used to test a capacitor according to one or moreembodiments disclosed herein. In one or more experiments, alternatingcurrent (AC) was used for testing the capacitor. In one or moreexperiments, direct current (DC) was used for testing the capacitor. Inone or more experiments in which AC at a 60 Hz frequency was employed,the material exhibited a decrease in resistance if voltage is in excessof 1000V. In one or more experiments, it was determined that theresistance is compromised particularly when an air pocket in the filmleads to the dielectric breakdown of air and the resistance dropsconsiderably as a low resistance path is created.

In one or more experiments in which DC of up to 100V was employed, thematerial was heated under bias. It was determined that this biasingaligned the molecules of the material, impacting the capacitance and theresistance in an advantageous way.

The Dielectric Constant:

In one or more experiments, the dielectric constant of the dielectricmaterial and capacitors disclosed herein was determined. The dielectricconstant was determined by relying on measured data and behavior of thecapacitors disclosed herein.

According to one or more embodiments, a capacitor having three (3)layers is provided. A first dielectric layer of suitable composition(21-1) is applied to the top electrode (16) and a second dielectriclayer of suitable composition (21-1) is applied to the bottom electrode(16). An inner layer (22) is provided that bridges the two dielectriclayers. In one or more embodiments, the first dielectric layer (21-1)and the second dielectric layer have different compositions. Arepresentative example of a capacitor according to one or moreembodiments is illustrated in FIG. 29.

In one or more experiments, it was determined that surface roughness ofthe dielectric has an impact in the capacitance. Specifically, when two(2) electrodes have been coated with the dielectric material and thendried fully under heat and vacuum, when they are mated together to buildthe capacitor, the small air pocket left at the interface may compromisethe capacitance and dielectric characteristics. For this reason and inorder to optimize results, various inner layers were tested to minimizeair pocket entrapment.

In one or more experiments, an inner layer was constructed using lowmolecular weight to high molecular weight polymers that exhibit highpolarity. In one or more embodiments, these polymers were doped withconductors, while in one or more additional embodiments, the polymersdid not contain a doping agent. In one or more embodiments, the polymersmay be a Cyano-Acrylate resin, Glycerol, carbon doped resin, graphenedoped resin, and a Cyano-Acrylate resin doped with chelating agent suchas TEA in order to bridge the air pocket at the interface and allow goodcapacitance build up in the capacitor. In one or more experiments, itwas determined that the addition of BaTiO3 increased the resistance ofthe dielectric material (21-5). The addition of BaTiO3 was varied frombetween about 0.1% by weight to about 20%. It was determined that atcompositions of about 20% by weight, the resistance increasedsignificantly while the capacitance decreased. According to one or moreembodiments, an advantageous range of BaTiO3 addition that increasedresistance and safeguarded capacitance was found to be between about 3%by weight and about 17% by weight. The dielectric (21-5) formulationused in this embodiment was composed of 20.9% by weight CopperPhthalocyanine, 3.0% by weight Zinc Phthalocyanine, 16.4% by weightBaTiO3, 56.7% by weight Texanol, and 3.0% by weight Glycerol. An innerlayer (22-2) consisting of a resin with high polarity doped with carbonwas placed between the two halves (see FIG. 30.)/The capacitor formedfrom the dielectric formulation was tested in terms of resistance as afunction of applied voltage. Subsequently, the capacitor was charged andthen measured for voltage decay.

In the one or more experiments, the results were unexpected in that theresistance and the capacitance exhibited a non-linear behavior. It wasalso determined that the leakage current is also non linear andgenerally low at low voltages and high at high voltages. Conversely, itwas determined that the resistance is high at low voltages and low athigh voltages.

In one or more experiments, it was determined that the lowering ofresistance with increased voltage is possibly due to the fact thatdielectric material disclosed herein made from a dispersion ofparticulates has many of its molecular dipoles align with the electricfield. In the presence of a high field gradient, as is the case within acapacitor, the mobility of any charged species contained with thedielectric is increased. The increase in mobility of charge species maybe the reason for the observed lowering of resistance and increasedleakage currents with higher voltages. Experimental results according tothe one or more experiments disclosed herein are illustrated in FIG. 31.

In one or more experiments, several chemistries were tested in terms ofresistance as a function of voltage. The results of these one or moreexperiments determined that resistance of these chemistries indicates astrong dependency on formulation. It was determined that the addition ofmismatched particles impacts the conductive path and increasesresistance. A good balance between high resistance having minimalleakage current and high capacitance having good charge build up isneeded to achieve best results. Experimental results are illustrated inFIG. 32. Demonstrate the dependency of charge storage on chemistry andformulation variations. In this particular example the best chemistry ofthe phthalocyanine particulates was composed of 25% CopperPhthalocyanine, 25% Zinc Phthalocyanine, 25% Magnesium Phthalocyanine,25% Nickel Phthalocyanine.

Metal Bridging Electrode:

In one or more experiments, an inner layer was constructed from ametallic electrode. The two (2) external electrodes were coated with adielectric material and partially dried. The inner metallic layer (22-3)was then placed in between the partially dried dielectric layers fromeach of the external electrodes. The capacitor formed is then clampedtogether and allowed to dry further. In one or more experiments, thecapacitors were tested in terms of resistance, leakage current andcharge storage and voltage decay. An exploded side view of the capacitoris illustrated in FIG. 33. A top view of the capacitor is illustrated inFIG. 34.

Current Measurement & Voltage Decay:

In one or more experiments, an ammeter was connected in series with thecapacitor to measure the current flowing through it during the chargingperiod. Since current flow decreases in the circuit as the capacitorscharge, this technique was effective in determining at which time thecapacitor was fully charged.

In one or more experiments, the capacitor is discharged by connectingthe volt meter in parallel to the capacitor and determining voltage dropas a function of time. Since the meter has a known resistance and thevoltage from the meter is an output signal that may be saved through adata acquisition board, the current flow that is outputted by thecapacitor may be calculated using the ratio of voltage to resistance.The cumulative current may also be integrated to determine the overallcharge accumulation and hence the capacitance. A circuit schematic of asystem used for charging and discharging the capacitors is illustratedin FIG. 35.

Voltage Decay:

Impact of Air Gaps/Defects at the Interface of 2 Mating Dielectric Films

The impact of interfacial defects at the interface of two (2) matingdielectric films is exemplified according to the one or more experimentsthat follow. Two (2) capacitors were built using identical electrodes inone experiment in which the capacitor was free of a bridging layer andin another experiment in which the capacitor has a bridging layer madeof a cyanoacrylate resin doped with carbon black. The drying process wascompleted so that no or almost no solvent was present in the dielectricfilm. The completed drying exacerbates the air pocket entrapmentdescribed before. Biasing was done at 2 volts at room temperature foreach of the two (2) capacitors. Experimental results depicting thevoltage decay for a capacitor using a bridging layer (referred to as“BL” in the Figures) in one of the capacitors and having no bridginglayer in another of the capacitors are illustrated in FIG. 36. FIG. 36illustrates the impact of air gaps at the interface of the dielectricfilms in which the voltage decay was substantial for the capacitorwithout the bridging layer compared to the capacitor with the bridginglayer. When the two halves of a capacitor are mated to form thecapacitor, the residual solvents help the capacitance to develop andadvantageous results may be obtained.

Charge Storage:

The slow voltage decay demonstrates that the dielectric film chemistrieshave the ability to store charges. This is significant in that thecapacitor has a battery like behavior or a capacitor like behaviordepending on the resistance that may be engineered within the film. Ineither case, the charge storage capability of the dielectric film madeof organic and organo-metallic particulates is advantageously high.

The impact of BaTiO3 Concentration:

In one or more experiments, the impact of the oxide dielectric materialon voltage decay was demonstrated. In one or more embodiments, theBaTiO3 concentration by volume was changed from about 3% to about 20%.As illustrated in the FIG. 37, the saturation current between thecapacitor was within range and the thickness of the film was 35 micronsper layer. The electrodes were Kovar for both data sets illustrated inFIG. 37. Both capacitors had the inner layer composition (carbon dopedresin) and thickness (35 microns).

Charging Under Heat and Bias:

In one or more experiments, a capacitor was formed by mating two (2)dielectric coated electrodes and having an inner-layer to bridge the airpocket at the mating interface. The capacitor was then charged under two(2) different biasing conditions and measured for voltage decay toquantify the capability of the technology to hold charge. The chargingcurrent flowing through a capacitor under a two (2) volt bias wasstabilized at 243 micro-amp. Subsequently to reaching currentsaturation, a voltage-decay through a voltmeter was performed. After thevoltage decay, the same capacitor was charged using a two (2) volt biaswhile being heated to 45° C. using an air gun to drive more current flowin the capacitor. Using this thermal treatment under a biasing voltagemay result in more charging of the capacitor. This may be demonstratedby the fact that the saturation current reached 43 micro-amps in theseone or more experiments which is much lower than the 243 micro-ampsobtained in the one or more experiments conducted under room temperaturebias. The voltage decay was measured and graphed in FIG. 38 whichillustrates that a slightly better result is obtained using heat andbias rather than just bias. Generally, the charging process is drivenfaster to completion in the presence of heat.

Charge Carriers:

In one or more experiments, it is determined that the increase incurrent flow brought about by the heat is most likely due to the factthat the mobility of charge carriers contained within the dielectric areable to flow more freely at slightly more elevated temperatures such as45° C. in this example. This may serve as proof that the organics andorgano-metallics contain charge carriers. The heat may also promotealignment of the dipoles contained within the dielectric. Thus the needfor controlled heating and controlled cooling in conducting the one ormore experiments disclosed herein.

Longer Voltage Decay:

In one or more experiments, the capacitor used in the one or moreexperiments referenced in the section entitled “Charging under heatbias” was recharged until a saturation current of 200 micro-amps wasachieved, and then a voltage decay measurement was preformed. In theseone or more experiments, the capacitor was not connected to a resistanceload. The results are illustrated in FIG. 39 in which a battery-likebehavior was demonstrated. The capacitor was charged using two (2) voltsand held charge for more than 48 hours since there was still charge leftinside. This discharge may be the result of the non-linear behaviorsince resistance increases with lower voltages and a residual permanentpolarization.

Impact of Electrodes:

In one or more experiments, Kovar electrodes were employed in buildingthe one or more capacitors described herein. In one or more additionalexperiments, aluminum electrodes were employed in building the one ormore capacitors described herein. In each of the relevant one or moreexperiments, the same or substantially the same dielectric chemistry wasused on both a pair of Kovar electrodes and a pair of aluminumelectrodes. It was observed that there were noticeable signs ofcorrosion on the aluminum electrodes. Experimental data is shown in FIG.40.

Impact of a Metal Bridging Layer:

In one or more experiments, the impact of a metallic bridging layer wasinvestigated. In the one or more experiments, Kovar electrodes wereused. The dielectric was applied to both the internal sides of theelectrodes and dried partially. The solvent left on the two (2)dielectric layers helped in making good contact with, or good wettingof, the inner metallic layer, which was also made of Kovar. Theillustration of the device is shown in FIG. 34. The voltage decay wastested and it was determined that the metallic layer was capable ofachieving a good voltage drop compared to the one or more embodiments inwhich the inner layer is made of an organic polymer. Experimentalresults are depicted in FIG. 41.

The Impact of Voltage Bias

In one or more experiments, a capacitor was first charged using a two(2) volt bias and then discharged during which time the voltage decaywas measured and recorded. Subsequent to the discharge, the capacitorwas charged a second time using a 23 volt bias and the voltage wassubsequently reduced to two (2) volts followed by a discharge. Thevoltage decay was measured again for this capacitor. It was determinedin one or more experimental results that there was no significantimprovement in voltage decay. It was determined that this is because thenovel dielectric material exhibits a strong non-linearity in behavior.Higher voltages used for biasing did lead to higher charge storage butnot in a linear fashion. The resistance drops to low values at highvoltages and results in higher internal leakage currents in thecapacitor. Experimental results are illustrated in FIG. 42.

In one or more experiments, it was determined that higher voltages usedfor biasing did lead to higher charge storage but only an incrementalincrease was observed and the increase was not linear. The resistancedrops to low values at high voltages leads to higher internal leakagecurrents in the capacitor. As illustrated in FIG. 43, the voltage dropsquickly to around two (2) volts where the resistance is high enough tominimize internal leakage currents. A fax ribbon coated with carbonblack was used as the inner layer. Part of the fax ribbon was cut anddip coated in a highly polar resin. Subsequently it was placed betweentwo electrodes coated with the novel dielectric and the charge storageand capacitance were maintained.

Cellulosic Paper

A porous paper was impregnated with the cyanoacrylate resin and innerlayered between two kovar electrodes having the novel dielectric. Thecapacitor worked well in terms of resistance, capacitance and chargestorage.

Active Versus Passive Metal Bridging Layers:

In one or more experiments, the biasing was performed using two (2)volts on the external metal electrodes. The metal inner layer had novoltage applied to it and is referred to herein as a passive metallayer. One external electrode was negatively charged and the oppositeelectrode was positively charged. In one or more additional experiments,a bias was applied to the internal metal layer in a symmetrical fashionvis-a-vis the external electrodes. In this manner, the internalelectrodes carry the same charge and the internal metal layer carriesthe opposite charge. It was determined that the charges were effectivelydoubled. FIGS. 44A and 44B illustrate the one or more capacitors madeaccording to the one or more experiments. It was determined that thevoltage decay is better behaved in the case of the passive metal layerand not in the case of the active metal layer as illustrated in theexperimental results shown in FIG. 45.

Dielectrics with Non-Linear Charge Drop with Gap or Voltage

In one or more experiments, it was determined that dielectrics may havereversed non-linearity. The one or more dielectrics disclosed herein mayhave a non-linear behavior in terms of applied voltage and the effectiveresistance is significantly higher with lower applied voltages. Theapplied electric field across the capacitor is related to the appliedvoltage divided by the distance between the electrodes. With theinsertion of the passive metal layer carrying no voltage, the presenceof the passive metal layer increases the effective distance of thecapacitor, and the electric field gradient is decreased by the additionof the passive metal layer. It was determined that this is the reasonwhy the dielectric separated by the passive layer exhibits bettervoltage decay since the resistance is in a higher regime and the chargebuild up is maintained due the lower leakage currents. For this reason,the spacing between the plates has a more favorable response in thisnovel non-linear dielectric as opposed to the standard dielectricmaterials. In conventional dielectrics, more applied voltage resulted inbetter charging until a dielectric breakdown threshold is reached. Theone or more capacitors disclosed herein are more appropriatelyconfigured than conventional dielectrics at lower voltages.

The one or more capacitors disclosed herein may be employed in multiplesin order to increase voltage or current, depending on the configuration.At a charging voltage of about two (2) volts in which the one or morecapacitors display advantageous characteristics, a multitude ofcapacitors could be employed to achieve battery-like behavior.Alternatively, serial addition of capacitor or dielectric thickness maybuild up voltage. For example, a ten (10) Volt capacitor battery may bebuilt using by stacking multiple capacitors in series.

A Combination of Organic and Metallic Bridging Layers

In one or more experiments, a combination of a metal and an organicbridging layer was employed in one or more capacitors. In one or moreembodiments, a resin doped with carbon was used as the organic innerlayer and Kovar was used as the metallic inner layer. A side view of theone or more capacitors is illustrated in FIG. 46A and a top view of theone or more capacitors is illustrated in FIG. 46B.

Voltage Build Up Through Stacking

In one or more experiments, in order to reach higher voltage outputwhile maintaining a large charge storage capability, a set of five (5)inner metal layers, referred to herein as metallic bridging layers, wereused between two (2) external electrodes that were under bias. Arepresentative example is illustrated as FIG. 47.

Voltage Decay Around 10V

The one or more capacitors referred to in the section entitled “VoltageBuild Up Through Stacking” were charged using a 100 Volt power supplyand then discharged through an HP meter. The experimental resultsshowing the voltage decay over time is illustrated in FIG. 48.

In one or more experiments, the charge up and discharge of a capacitoraccording to one or more embodiments was performed. The discharge orvoltage decay was done through the meter, then through a 50 K-OHM and a20 K-OHM resistance load. Experimental results of the one or moreexperiments are illustrated in FIG. 49. As illustrated, the voltagethrough the meter was around 10 Volts and decreased over time for thedecay through the meter. A lower voltage was observed through a 50 K-OHMand a 20 K-OHM resistance load. It was determined that this suggeststhat a higher resistance is better suited for discharging the ultracapacitor.

In one or more experiments, a comparison between the ultra-capacitor anda commercially available 220 micro-farad electrolytic capacitor wasperformed. The discharge was done through a 20 K-OHM resistance load inone or more experiments illustrated in FIG. 50 and through a 50 K-OHMresistance load in one or more experiments illustrated in FIG. 51.

The Charge Storage

The charge storage is directly related to the current flowing throughthe resistive load. Since the voltage decay is measured through a knownresistive load, the current flowing through the load can be calculatedby the ratio of voltage and resistance at any given point in timethrough the discharge period. In one or more experiments, the currentflow through the resistive load through for the one or more capacitorsreferred to in the section entitled “Voltage Build Up Through Stacking”was measured and contrasted against an electrolytic capacitor. Theexperimental results are illustrated in FIG. 52.

The Cumulative Charge

In one or more experiments, the current flow through a resistive loadper unit time for the one or more capacitors referred to in the sectionentitled “Voltage Build Up Through Stacking” was integrated over aperiod of five (5) minutes and contrasted with the current flow througha resistive load per unit time for the electrolytic capacitor. Theexperimental results are illustrated in FIG. 53.

Discharge Through a Higher Resistive Load

In one or more experiments, the charge up of the one or more capacitorsreferred to in the section entitled “Voltage Build Up Through Stacking”using 100 Volts was performed followed by a discharge or voltage decaythrough the meter, then through a 500 K-OHM resistance load and a 100K-OHM resistance load. Experimental results are illustrated in FIGS. 54and 55. As illustrated, the voltage through the meter was around ten(10) Volts and decreased over time. A lower voltage was observed througha 100 K-OHM resistance load and a 500 K-OHM resistance load. It wasdetermined that a higher resistance load is better suited fordischarging the one or more capacitors as higher current flow isobserved. FIG. 55 illustrates the integration of current and time.

Measuring Charging Current

In one or more experiments, one or more capacitors were built usingseven (7) metal inner layers. In these one or more experiments, the oneor more capacitors were charged and measured per unit time. The currentflow into the one or more capacitors was measured and integrated toyield the current that flowed into the capacitor. This current was thencontrasted with the charging current that went into a 1000 mF capacitor.In this manner, the charge storage capacitor of the one or morecapacitors could be compared to a known charge storage capacity.Experimental results are illustrated in FIGS. 56 through 59.

Voltage-Build Up Through a Stack Up Having a 7 Metal LayerUltra-Capacitor:

In one or more experiments, various voltage decay measurements wereperformed on the one or more capacitors using seven (5) metal innerlayers to illustrate the buildup of charge as a function of voltage.Biasing takes place from the outer most electrodes and the voltage isdistributed across the various electrodes as illustrated in FIG. 60.Experimental results are illustrated in FIG. 61 in which the biasing wasdone at various voltages on the external electrodes. In one or moreexperiments, the net voltage between adjacent electrodes is divided bythe number of metal layers, resulting in a lower voltage operationalregime where resistance is high and capacitance is high and leakagecurrent is minimal. However, the capacitor needs a high biasing voltagefor a good charge build up to be achieved. There is a capacitance and aresistance that builds up between any two (2) inner metal layers. Theeffective resistance of the system is the sum total of the resistancespresented between each of the metal layers which happen to be configuredin series. Since the resistance is high, more voltage is needed to drivemore current. Conversely, the voltage decay following the biasing stepsshould exhibit a dependency of the biasing voltage. As illustrated inFIG. 61, the voltage decay is higher when biasing is performed at 50V,which in turn in higher than biasing preformed at 11V, which in turn ishigher for biasing performed at 5V.

Since more voltage is needed to drive more charging current into the oneor more capacitors using seven (5) metal inner layers, the middleelectrode was used as the positive pole and the two (2) externalelectrodes were used as the negative poles as illustrated in the FIG.62. Since the biasing takes place from the outer most electrodes and thecenter electrode, the applied voltage is distributed across two (2) setsof ultra-capacitors each having three (3) inner metallic layers. Inthese one or more experiments, the applied voltage is divided by thethree (3) inner metallic layers and the resistance of the system is cutin half.

These one or more biasing configurations allow for doubling the voltagebetween adjacent electrodes since the same voltage is applied throughhalf as many inner metallic layers. The resistance is cut in half sincethere are only half as many series of resistances between adjacentelectrodes for the same applied voltage. It was determined that thiseffectively quadrupled the current.

In one or more experiments, the voltage decay through a known resistiveload enabled measurement of the current per unit time going through theload at any given time. In one or more experiments, the current was thenintegrated to yield the charge release in mA-sec as a function of time.As can be illustrated in FIG. 63, more current was stored in anddischarged from the one or more capacitors that were charged using acenter inner metal layer as a biasing pole compared to the one or morecapacitors that were biased across its external electrodes.

The novel dielectric enables a novel fully integrated PV device that hasthe novel-supercapacitor device attached to it. A typical design wouldrequire the PV solar cell. The supercapacitor can be mounted or built onthe backside electrode (28) in FIG. 64. The design is such that the TCOupper electrode (31), a semiconductor junction material (30) on top of ap-type or n-type semiconductor substrate (29) is connected in parallelwith the supercapacitor with a safety diode placed to prevent backcurrent through the solar cell. The diagram shows the backside electrode(28) serving as one of the direct supports for one of the supercapacitorelectrodes. The other is mounted on the other side of a perimeter spacer(27) that permits addition of the electrolyte. Low cost requires thatthe supercapacitor electrodes be fabricated by a process that is fullycompatible with the manufacturing process for the PV film stack. Metalcontacts and electrodes can be deposited using the same processes as inPV manufacturing. A representative example according to one or moreembodiments is illustrated in FIG. 64.

While the embodiments have been described in connection with thepreferred embodiments of the various figures, it is to be understoodthat other similar embodiments may be used or modifications andadditions may be made to the described embodiment for performing thesame function without deviating therefrom. Therefore, the disclosedembodiments should not be limited to any single embodiment, but rathershould be construed in breadth and scope in accordance with the appendedclaims.

What is claimed:
 1. A dielectric material comprising: at least one layerof material comprising: organometallic particles in a substantiallycontinuous phase; and wherein the organometallic particles comprisestacked organometallic molecules, and wherein the organometallicparticles include a first size of particles and a second size ofparticles.
 2. The dielectric material of claim 1, wherein a chemistry ofeach of the organometallic molecules is formed of a complex of a metalwith an organic molecule having delocalized electrons.
 3. The dielectricmaterial of claim 1, wherein a substantial number of the organometallicparticles are electrically connected.
 4. The dielectric material ofclaim 1, wherein the organometallic particles are embedded in an organicmatrix.
 5. The dielectric material of claim 1, wherein a substantialnumber of the organometallic particles are crystalline and comprise atleast one organometallic crystal formed of stacked organometallicmolecules.
 6. The dielectric material of claim 1, wherein organometallicparticles comprise metal-phthalocyanine particles.
 7. The dielectricmaterials of claim 6, wherein the metal-phthalocyanine particles areselected from the group consisting of copper-phthalocyanine,zinc-phthalocyanine, magnesium-phthalocyanine, nickel-phthalocyanine,lead-phthalocyanine, iron-phthalocyanine and combinations thereof. 8.The dielectric material of claim 5, wherein the organometallic particlesare crystalline and comprise at least one metal-phthalocyanine crystalformed of stacked metal phothlocyanine molecules.
 9. The dielectricmaterial of claim 2, wherein the continuous phase material comprises asecond dielectric material in dispersed form.
 10. The dielectricmaterial of claim 8, wherein the second dielectric material is selectedfrom the group consisting of BaTiO3, ferroelectric, relaxor dielectric,alumina, silica, activated silica, alkali aluminosilicates, alkalinealuminosilicates and zeolites.
 11. The dielectric material of claim 1,wherein the at least one layer of material comprises a first layer and asecond layer, the first layer comprising the first type oforganometallic particle, and the second layer comprising the second typeof organometallic particle.
 12. An energy storage device comprising athickness of the dielectric material according to claim 1 and twoelectrodes disposed substantially on opposite surfaces of the at leastsingle layer dielectric material.
 13. The energy storage device of claim12, wherein the electrodes are made of conductive materials includingmetals, metal alloys, carbon base conductors, graphene, activatedcarbon, carbon-nano-tubes, conductive polymers and organic polymersdoped with carbon base conductors and metals, conductive materials withhigh surface area and high porosity, composited electrodes made of acombination of these materials.
 14. The energy storage device of claim13 wherein the dielectric material contains at least two layers, eachlayer formed of material from the group consisting of organometallicparticles in substantially continuous form, and wherein the at least twolayers further comprise an inner layer disposed between each of the atleast two layers and said inner layer has conductive and/orsemi-conductive layer.
 15. The energy storage device of claim 14,wherein said inner layer is made of a viscous organic based materialfrom having a high polarity and doped with conductive materialsincluding silver, copper, gold, graphene, activated carbon, conductivepolymers and other conductive materials and material combinations.